KR20220095186A - Resin composition, resin film, laminate, coverlay film, copper foil containing resin, metal clad laminate and circuit board - Google Patents

Abstract

(A) Diamine containing 40 mol% or more of a dimer diamine composition comprising a tetracarboxylic anhydride component and a dimer diamine in which two terminal carboxylic acid groups of the dimer acid are substituted with primary aminomethyl groups or amino groups with respect to the total diamine component A resin composition comprising a thermoplastic resin containing a structural unit derived from a component, and (B) at least one selected from aromatic condensed phosphate ester, silica particles, or liquid crystalline polymer filler.

Description

Resin composition, resin film, laminate, coverlay film, copper foil containing resin, metal clad laminate and circuit board

The present invention relates to a resin composition useful as an adhesive in a circuit board such as a printed wiring board, a resin film, a laminate, a coverlay film, a resin-containing copper foil, a metal clad laminate, and a circuit board using the same.

In recent years, with the progress of miniaturization, weight reduction, and space saving of electronic devices, a flexible printed wiring board that is thin, lightweight, flexible, and has excellent durability even after repeated bending. The demand for flexible printed circuits (FPCs) is increasing. Since the FPC can be mounted in a three-dimensional and high-density manner even in a limited space, for example, wiring of movable parts of electronic devices such as HDDs, DVDs, and mobile phones, cables, connectors, etc. Its use is expanding to parts.

In addition to the above-mentioned densification, as the performance of equipment progresses, it is also necessary to cope with the increase in the frequency of transmission signals. In information processing and information communication, in order to transmit and process large-capacity information, the transmission frequency is increased, and in the printed circuit board material, thinning of the insulating layer and improvement of the dielectric properties of the insulating layer are made. A reduction in transmission loss is required. In the future, FPCs and adhesives corresponding to higher frequencies are required, and reduction of transmission loss becomes important.

For example, in millimeter wave transmission, which is one of 5G transmission, a direct conversion method in which millimeter waves directly flow to the FPC connecting the antenna and the substrate is being considered. Since the milli-wave band has a higher frequency than the conventional communication frequency, and the dielectric loss in transmission loss becomes larger, improvement of the dielectric properties of the insulating resin layer becomes more important. As a technique for improving the dielectric properties of the insulating resin layer of a circuit board, it has been proposed to mix liquid crystalline polymer particles with a thermoplastic resin or a thermosetting resin (Patent Document 1). However, in Patent Document 1, there are no examples other than the epoxy resin, and detailed examination of the thermoplastic resin has not been made. Further, it has been proposed to reduce the coefficient of thermal expansion and the relative dielectric constant by blending silica particles with a polyimide-based resin used as an insulating resin layer of a circuit board (Patent Document 2, Patent Document 3).

By the way, as a technology related to an adhesive layer containing polyimide as a main component, a polyimide using a diamine compound derived from an aliphatic diamine such as dimer acid (dimer fatty acid) as a raw material, and at least two primary amino groups It has been proposed to apply a crosslinked polyimide resin obtained by reacting an amino compound having as a functional group to an adhesive layer of a coverlay film (for example, Patent Document 4). Also, it has been proposed to apply a resin composition in which a thermosetting resin such as a polyimide and an epoxy resin and a crosslinking agent are used together to a copper clad laminate (for example, Patent Document 5). Moreover, it is also proposed to make a low dielectric loss tangent and a flame retardance compatible by mix|blending the metal salt of organic phosphinic acid with the polyimide using dimer acid type diamine (patent document 6). However, in Patent Documents 4 to 6, the influence of by-products other than dimerdiamine derived from the dimer acid contained in the raw material is not considered at all.

Dimer acid is obtained by, for example, a Diels-Alder reaction using natural fatty acids such as soybean oil fatty acid, tall oil fatty acid, rapeseed oil fatty acid, and purified oleic acid, linoleic acid, linolenic acid, erucic acid, etc. It is the dimerized fatty acid obtained, and it is known that the polybasic acid compound derived from a dimer acid is obtained as a composition of the fatty acid which is a raw material, or the fatty acid more than trimerization (for example, patent document 7).

Patent Document 1: Japanese Patent No. 6295013 Publication 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

Thermoplastic resins such as polyimide using aliphatic diamine compounds such as dimerdiamine as raw materials (hereinafter, may be referred to as "aliphatic thermoplastic resin") have room for improvement in flame retardancy, but have low dielectric loss tangent and The resin which is provided with flexibility and crosslinked this is a material which has heat resistance and adhesiveness at the same time. From this, the aliphatic thermoplastic resin is expected as a material for high-speed transmission FPC applications whose usage is increasing due to the spread of 5G communication. On the other hand, since the frequency of the signal flowing through the FPC is expected to become higher in the future, a material based on an aliphatic thermoplastic resin and having better dielectric properties is required.

In addition, as a means of controlling the physical properties of a resin containing polyimide as a main component, it is important to control the molecular weight of polyamic acid or polyimide, which is a precursor of polyimide. However, in the case of applying dimerdiamine as a raw material, it is used in a state including by-products other than dimerdiamine derived from dimer acid. These by-products not only make it difficult to control the molecular weight of polyimide, but also affect the dielectric properties in a wide frequency range and its humidity dependence.

Accordingly, a first object of the present invention is to provide a resin composition and a resin film capable of responding to the high frequency of electronic devices by further improving the dielectric properties of the aliphatic thermoplastic resin. A second object of the present invention is to provide a resin composition and a resin film capable of responding to the high frequency of electronic devices by improving dielectric properties while using dimerdiamine as a raw material.

The resin composition of this invention is following (A) component and (B) component;

(A) A structure derived from a diamine component containing 40 mol% or more of a dimerdiamine composition containing as a main component dimerdiamine in which two terminal carboxylic acid groups of dimer acid are substituted with primary aminomethyl groups or amino groups with respect to the total diamine component a thermoplastic resin containing units, and

(B) at least one selected from aromatic condensed phosphate esters, silica particles, or liquid crystalline polymer fillers

contains

The resin composition of the present invention may be a polyimide in which the component (A) is made by reacting a tetracarboxylic acid anhydride component with a diamine component containing 40 mol% or more of the dimer diamine composition with respect to the total diamine components. B) The said aromatic condensed phosphoric acid ester may be sufficient as a component. In this case, the weight ratio of the said (B) component with respect to the said (A) component may exist in the range of 0.05-0.7, Preferably it may exist in the range of 0.2-0.5. Moreover, the weight ratio of the phosphorus derived from the aromatic condensed phosphate ester of the said (B) component with respect to the said (A) component may exist in the range of 0.01-0.1. Moreover, the weight ratio of the phosphorus derived from the aromatic condensed phosphate ester of the said (B) component with respect to the dimerdiamine composition in the said (A) component may exist in the range of 0.01-0.15.

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

In the resin composition of the present invention, the component (A) may be a polyamic acid or polyimide obtained by reacting a tetracarboxylic acid anhydride component with a diamine component containing 40 mol% or more of the dimer diamine composition with respect to all diamine components. Moreover, the silica particle provided with a cristobalite crystal phase or a quartz crystal phase may be sufficient as said (B) component. In this case, the said (B) component is within the range of 5 to 60 weight% with respect to the total of the said (A) component (however, polyamic acid is converted into imidated polyimide) and the said (B) component. it's good too Moreover, the silica particle of the said (B) component is a cristobalite crystal phase and a quartz crystal phase with respect to the total area of all the peaks derived from SiO2 in _the range of 2θ=10° to 90° of the X-ray diffraction spectrum by CuKα ray. The ratio of the total area of the derived peaks may be 20 weight% or more. In addition, the silica particles of the component (B) have an average particle diameter D ₅₀ of 6 to 20 μm, at which the cumulative value in the frequency distribution curve obtained by volume-based particle size distribution measurement by the laser diffraction scattering method is 50%. It may be within the range.

The resin composition of the present invention may be a polyimide in which the component (A) is made by reacting a tetracarboxylic acid anhydride component with a diamine component containing 40 mol% or more of the dimer diamine composition with respect to the total diamine components. B) The component may be the liquid crystalline polymer filler. In this case, the said (B) component may exist in the range of 15-50 volume% with respect to the sum total of the said (A) component and the said (B) component. Further, when the dielectric loss tangent at 10 GHz of the component (A) is Dfa, and the dielectric loss tangent at 10 GHz of the liquid crystalline polymer filler of the component (B) is Dfb, Dfb may be less than 0.0019, and Dfa > Dfb. In addition, with respect to 100% by weight of the nonvolatile organic compound component of the resin composition, 15 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) contains 90 mole parts or more in total of tetracarboxylic acid anhydride represented by the following general formulas (1) and/or (2) with respect to 100 mole parts of the tetracarboxylic acid anhydride component, also good

[Formula 1]

In the general formula (1), X represents a single bond or a divalent group selected from the following formulae, and in the general formula (2), the cyclic moiety represented by Y is a 4-membered ring, a 5-membered ring, a 6-membered ring, a 7-membered ring or an 8-membered ring. indicates that a cyclic saturated hydrocarbon group selected from

[Formula 2]

In the above formula, Z represents —C ₆ H ₄ —, —(CH ₂ )n— or —CH ₂ —CH(—O—C(=O)—CH ₃ )—CH ₂ —, and n is 1 An integer of -20 is represented.

The resin film of the present invention is a resin film comprising a thermoplastic resin layer, the following (A) component and (B) component;

(A) A structure derived from a diamine component containing 40 mol% or more of a dimerdiamine composition containing as a main component dimerdiamine in which two terminal carboxylic acid groups of dimer acid are substituted with primary aminomethyl groups or amino groups with respect to the total diamine component a thermoplastic resin containing units, and

(B) at least one selected from aromatic condensed phosphate esters, silica particles, or liquid crystalline polymer fillers

contains

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

In the resin film of the present invention, when the component (B) consists of silica particles having a cristobalite crystal phase or a quartz crystal phase, the content thereof is 3 to the total of the component (A) and the component (B). You may exist in the range of 41 volume%.

In the resin film of the present invention, when the component (B) is composed of the liquid crystalline polymer filler, its content is within the range of 15 to 40% by volume based on the total of the component (A) and the component (B). good night.

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

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

In the resin-containing copper foil of the present invention, an adhesive layer and a copper foil are laminated, and the adhesive layer is made of the resin film.

The metal clad laminate of the present invention includes an insulating resin layer and a metal layer laminated on at least one surface of the insulating resin layer, wherein at least one of the insulating resin layers is made of the resin film.

The circuit board of the present invention is formed by wiring the metal layer of the metal clad laminate.

Since the resin composition of the present invention contains component (A) and component (B), a resin film formed using this has excellent dielectric properties and flexibility derived from dimerdiamine, and contains component (B) has improved dielectric properties. Therefore, the resin composition and the resin film of the present invention can be particularly suitably used as a material for circuit boards such as FPC in, for example, electronic devices requiring high-speed signal transmission.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described.

The resin composition of 1 Embodiment of this invention is following (A) component and (B) component;

(A) A structure derived from a diamine component containing 40 mol% or more of a dimerdiamine composition containing as a main component dimerdiamine in which two terminal carboxylic acid groups of dimer acid are substituted with primary aminomethyl groups or amino groups with respect to the total diamine component a thermoplastic resin containing units, and

(B) at least one selected from aromatic condensed phosphate esters, silica particles, or liquid crystalline polymer fillers

contains

[(A) component; thermoplastic resin]

The thermoplastic resin of component (A) refers to a dimer diamine composition containing as a main component dimer diamine in which two terminal carboxylic acid groups of dimer acid are substituted with primary aminomethyl groups or amino groups with respect to all diamine components 40 mol% or more A resin containing a structural unit derived from a diamine component contained therein, the maximum value of the loss tangent (tanδ) measured using a dynamic viscoelasticity measuring device (DMA) means a resin of less than 200 ° C. . Therefore, as the thermoplastic resin, a diamine component containing 40 mol% or more of the dimerdiamine composition is used as a raw material, and a thermoplastic polyimide, a polyamic acid precursor thereof, a thermoplastic bismaleimide resin, a thermoplastic epoxy resin, a thermoplastic polyamide resin, their hardened|cured material etc. are mentioned. These thermoplastic resins can be mix|blended in combination of 2 or more type. Among these thermoplastic resins, the tetracarboxylic acid anhydride component and the dimer diamine composition containing as a main component a dimer diamine in which two terminal carboxylic acid groups of the dimer acid are substituted with primary aminomethyl groups or amino groups with respect to the total diamine component are 40 mol% or more. More preferable are a thermoplastic polyimide (hereinafter, sometimes referred to as "DDA-based thermoplastic polyimide") obtained by imidizing a polyamic acid, which is a precursor obtained by reacting a diamine component, and a crosslinked cured product thereof.

Hereinafter, as a representative example of a thermoplastic resin, a DDA-type thermoplastic polyimide is given and demonstrated in detail.

In addition, although "thermoplastic polyimide" is generally a polyimide whose glass transition temperature (Tg) can be clearly confirmed, in the present invention, the storage modulus at 30°C measured using a dynamic viscoelasticity measuring device (DMA) (貯藏彈性率) is 1.0×10 ⁸ Pa or more, and refers to a polyimide having a storage modulus at 300° C. of less than 3.0×10 ⁷ Pa. In addition, "non-thermoplastic polyimide" is generally a polyimide that does not show softening or adhesion even when heated, but in the present invention, the storage modulus at 30°C measured using a dynamic viscoelasticity measuring device (DMA) is 1.0× It is 10 ⁹ Pa or more and refers to a polyimide having a storage modulus at 300°C of 3.0×10 ⁸ Pa or more.

<DDA-based thermoplastic polyimide>

DDA-based thermoplastic polyimide is an aliphatic thermoplastic polyimide, which is highly flexible, has sufficient toughness even when a large amount of liquid crystalline polymer filler is added, and maintains its shape when a resin film is formed. high ability to Therefore, it is preferable that 60 weight% or more is preferable, as for the content rate of the DDA-type thermoplastic polyimide in (A) component, 70 weight% or more is more preferable, and 80 weight% or more is the most preferable. (A) When the content rate of the DDA type|system|group thermoplastic polyimide in component is less than 60 weight%, the toughness of a thermoplastic resin will fall, and film retentivity at the time of forming a resin film will fall.

The DDA-based thermoplastic polyimide contains a tetracarboxylic acid residue derived from tetracarboxylic acid anhydride as a raw material and a diamine residue derived from a diamine compound as a raw material. By reacting the raw material tetracarboxylic anhydride and the diamine compound in substantially equimolar amounts, the types and amounts of tetracarboxylic acid residues and diamine residues contained in the DDA-based thermoplastic polyimide can be substantially matched to the type and amount of the raw material.

(Tetracarboxylic acid anhydride component)

For the DDA-based thermoplastic polyimide, as a raw material, tetracarboxylic anhydride generally used for thermoplastic polyimide can be used without any particular limitation, but with respect to all tetracarboxylic acid anhydride components, the following general formulas (1) and/or (2) It is preferable to contain a total of 90 mol% or more of the tetracarboxylic anhydride shown. That is, the DDA-based thermoplastic polyimide contains 90 mole parts or more in total of tetracarboxylic acid residues derived from tetracarboxylic acid anhydrides represented by the following general formulas (1) and/or (2) with respect to 100 mole parts of total tetracarboxylic acid residues. desirable. Coexistence of flexibility and heat resistance of DDA-based thermoplastic polyimide by containing 90 mol parts or more in total with respect to 100 mol parts of tetracarboxylic acid residues derived from tetracarboxylic acid anhydride represented by the following general formulas (1) and/or (2) This is preferable because it is easy. When the total amount of tetracarboxylic acid residues derived from tetracarboxylic acid anhydride represented by the following general formulas (1) and/or (2) is less than 90 mol parts, the solvent solubility of the DDA-based thermoplastic polyimide tends to decrease.

[Formula 3]

In the general formula (1), X represents a single bond or a divalent group selected from the following formula, and in the general formula (2), the cyclic moiety represented by Y is a 4-membered ring, a 5-membered ring, a 6-membered ring, or 7 It represents that a cyclic saturated hydrocarbon group selected from a membered ring or an 8 membered ring is formed.

[Formula 4]

In the above formula, Z represents —C ₆ H ₄ —, —(CH ₂ )n— or —CH ₂ —CH(—O—C(=O)—CH ₃ )—CH ₂ —, and n is 1 An integer of -20 is represented.

Examples of the tetracarboxylic anhydride represented by the general formula (1) include 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), 3,3',4,4'-benzophenonetetracarboxylic acid dianhydride (BTDA), 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride (DSDA), 4,4'-oxydiphthalic anhydride (ODPA), 4,4'-(hexafluoroiso Propylidene) diphthalic anhydride (6FDA), 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride (BPADA), p-phenylene bis (trimellitic acid monoester acid anhydride) ) (TAHQ), ethylene glycol bisanhydro trimellitate (TMEG), etc. are mentioned. Among these, 3,3',4,4'-benzophenonetetracarboxylic dianhydride (BTDA) is especially preferable. In the case of using BTDA, since the carbonyl group (ketone group) provides adhesiveness, the decrease in peel strength when a liquid crystalline polymer filler is added as component (B) is suppressed, and the adhesiveness of the DDA-based thermoplastic polyimide is improved. can be improved In addition, in BTDA, the ketone group present in the molecular skeleton and the amino group of an amino compound for crosslinking described later react to form a C=N bond in some cases, and the effect of improving heat resistance is likely to be expressed. From this point of view, it is preferable to contain at least 50 molar parts, more preferably at least 60 molar parts, of the tetracarboxylic acid moiety derived from BTDA with respect to 100 molar parts of the tetracarboxylic acid moiety.

Further, examples of the tetracarboxylic anhydride represented by the general formula (2) include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2, 4,5-cyclohexanetetracarboxylic dianhydride, 1,2,4,5-cycloheptanetetracarboxylic dianhydride, 1,2,5,6-cyclooctane tetracarboxylic dianhydride, etc. are mentioned.

The DDA-based thermoplastic polyimide may contain a tetracarboxylic acid residue derived from an acid anhydride other than the tetracarboxylic acid anhydride represented by the general formulas (1) and (2) in the range not impairing the effects of the invention. Although there is no particular limitation on the tetracarboxylic acid residue, for example, pyromellitic dianhydride, 2,3',3,4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'- or 2,3 ,3',4'-benzophenonetetracarboxylic dianhydride, 2,3',3,4'-diphenyl ether tetracarboxylic dianhydride, bis(2,3-dicarboxyphenyl)ether dianhydride, 3,3'' ,4,4''-, 2,3,3'',4''- or 2,2'',3,3''-p-terphenyltetracarboxylic dianhydride, 2,2-bis(2, 3- or 3,4-dicarboxyphenyl)-propanedianhydride, bis(2,3- or 3,4-dicarboxyphenyl)methandianhydride, bis(2,3- or 3,4-dicarboxyphenyl) Sulfonic anhydride, 1,1-bis (2,3- or 3,4-dicarboxyphenyl) ethane dianhydride, 1,2,7,8-, 1,2,6,7- or 1,2,9 , 10-phenanthrene-tetracarboxylic dianhydride, 2,3,6,7-anthracene tetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) tetrafluoropropane dianhydride, 1,2, 5,6-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 4,8-dimethyl-1,2,3, 5,6,7-hexahydronaphthalene-1,2,5,6-tetracarboxylic dianhydride, 2,6- or 2,7-dichloronaphthalene-1,4,5,8-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-, 3,4,9,10-, 4,5,10,11- or 5,6,11,12-perylene-tetracarboxylic dianhydride, pyrazine-2,3,5,6-tetracarboxylic acid Dianhydride, pyrrolidine-2,3,4,5-tetracarboxylic dianhydride, thiophene-2,3,4,5-tetracarboxylic dianhydride, 4,4'-bis(2,3-dicarboxyphenoxy) C) and tetracarboxylic acid residues derived from aromatic tetracarboxylic dianhydrides such as diphenylmethane dianhydride.

(diamine component)

The DDA-based thermoplastic polyimide uses, as a raw material, a diamine component containing 40 mol% or more of the dimer diamine composition, more preferably 60 mol% or more, based on all the diamine components. By containing the dimerdiamine composition in the above amount, the dielectric properties of the polyimide are improved, and the thermocompression bonding properties are improved by lowering the glass transition temperature (lower Tg) of the polyimide and the interior by lowering the elastic modulus stress can be relieved.

(dimerdiamine composition)

The dimerdiamine composition contains the following component (a) as a main component, and the quantity of a component (b) and a component (c) is controlled.

(a) dimerdiamine;

(a) The dimer diamine of the component refers to a diamine in which two terminal carboxylic acid groups (-COOH) of the dimer acid are substituted with a primary aminomethyl group (-CH ₂ -NH ₂ ) or an amino group (-NH ₂ ). it means. Dimer acid is a well-known dibasic acid obtained by intermolecular polymerization of unsaturated fatty acids, and its industrial production process is almost standardized in the industry, and dimerization of unsaturated fatty acids having 11 to 22 carbon atoms using a clay catalyst or the like. obtained by reconciliation. The industrially obtained dimer acid is mainly composed of a dibasic acid having 36 carbon atoms obtained by dimerizing an unsaturated fatty acid having 18 carbon atoms such as oleic acid, linoleic acid, and linolenic acid. (C54) and another polymerized fatty acid having 20 to 54 carbon atoms. In addition, although a double bond remains after the dimerization reaction, in the present invention, the dimer acid also includes a hydrogenation reaction to reduce the degree of unsaturation. The dimer diamine of component (a) can be defined as a diamine compound obtained by substituting a primary aminomethyl group or an amino group for the terminal carboxylic acid group of a dibasic acid compound having 18 to 54 carbon atoms, preferably 22 to 44 carbon atoms. have.

As a characteristic of dimerdiamine, the characteristic derived from the backbone of a dimer acid can be provided. That is, since dimerdiamine is an aliphatic macromolecule having a molecular weight of about 560 to 620, the molar volume of the molecule can be increased to relatively reduce the polar group of the DDA-based thermoplastic polyimide. The characteristics of such dimer acid-type diamine are considered to contribute to improving dielectric properties by reducing the relative dielectric constant and dielectric loss tangent while suppressing a decrease in the heat resistance of the DDA-based thermoplastic polyimide. In addition, since it has two free-moving minor chains having 7 to 9 carbon atoms and two chain aliphatic amino groups having a length close to 18 carbon atoms, it not only gives flexibility to the DDA-based thermoplastic polyimide, but also Rather, since the DDA-based thermoplastic polyimide can have an asymmetric chemical structure or a non-planar chemical structure, it is considered that the dielectric constant can be reduced.

The dimerdiamine composition is obtained by increasing the dimerdiamine content of component (a) to 96% by weight or more, preferably 97% by weight or more, more preferably 98% by weight or more by a purification method such as molecular distillation. good to use (a) By making dimerdiamine content of component 96 weight% or more, dispersion|distribution of molecular weight distribution of a DDA type|system|group thermoplastic polyimide can be suppressed. Also, if technically possible, it is best that all (100% by weight) of the dimerdiamine composition is composed of the dimerdiamine of component (a).

(b) a monoamine compound obtained by substituting a terminal carboxylic acid group of a monobasic acid compound having 10 to 40 carbon atoms with a primary aminomethyl group or an amino group;

The monobasic acid compound having 10 to 40 carbon atoms includes a monobasic unsaturated fatty acid having 10 to 20 carbon atoms derived from the raw material of dimer acid and a by-product in the production of dimer acid having 21 to 40 carbon atoms. It is a mixture of monobasic acid compounds in The monoamine compound is obtained by substituting a terminal carboxylic acid group of these monobasic acid compounds with a primary aminomethyl group or an amino group.

(b) The monoamine compound of a component is a component which suppresses the molecular weight increase of a polyimide. During polymerization of polyamic acid or polyimide, the monofunctional amino group of the monoamine compound reacts with the terminal acid anhydride group of the polyamic acid or polyimide, whereby the terminal acid anhydride group is sealed and the polyamic acid or polyimide inhibit the increase in molecular weight of

(c) an amine compound obtained by substituting a terminal carboxylic acid group of a polybasic acid compound having a hydrocarbon group within the range of 41 to 80 carbon atoms with a primary aminomethyl group or an amino group (however, the dimerdiamine is excluded);

The polybasic acid compound having a hydrocarbon group in the range of 41 to 80 carbon atoms is a polybasic acid compound mainly comprising a tribasic acid compound in the range of 41 to 80 carbon atoms, which is a by-product in the production of dimer acid. Moreover, polymerized fatty acids other than a C41-C80 dimer acid may be included. The amine compound is obtained by substituting a terminal carboxylic acid group of these polybasic acid compounds with a primary aminomethyl group or an amino group.

(c) The amine compound of a component is a component which promotes the molecular weight increase of a polyimide. A trifunctional or higher amino group containing a triamine derived from trimer acid as a main component reacts with a terminal acid anhydride group of a polyamic acid or polyimide to rapidly increase the molecular weight of the polyimide. 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 polyimides and cause gelation of polyamic acids or polyimides.

The dimerdiamine composition is, when quantification of each component by measurement using gel permeation chromatography (GPC), the peak start, peak top and peak end of each component of the dimerdiamine composition can be easily identified For this, a sample in which the dimerdiamine composition was treated with acetic anhydride and pyridine is used, and cyclohexanone is used as an internal standard. Using the thus prepared sample, each component is quantified by area percent of the chromatogram of GPC. The peak start and peak end of each component are taken as the minimum values of each peak curve, and the area percent of the chromatogram can be calculated based on this.

In the dimerdiamine composition used in the present invention, the total of the components (b) and (c) is 4% or less, preferably less than 4%, in terms of area percent of the chromatogram obtained by GPC measurement. By making the sum total of a component (b) and a component (c) into 4 % or less, dispersion|distribution of molecular weight distribution of a polyimide can be suppressed.

Moreover, as for the area percent of the chromatogram of (b) component, Preferably it is 3 % or less, More preferably, it is 2 % or less, More preferably, 1 % or less is good. By setting it as such a range, the fall of the molecular weight of a polyimide can be suppressed and the range of the addition molar ratio of a tetracarboxylic anhydride component and a diamine component can be broadened. In addition, (b) component does not need to be contained in dimerdiamine composition.

Moreover, the area percent of the chromatogram of (c)component is 2 % or less, Preferably it is 1.8 % or less, More preferably, 1.5 % or less is good. By setting it as such a range, the rapid increase of the molecular weight of polyimide can be suppressed and also the raise of the dielectric loss tangent in the frequency range of a resin film can be suppressed. In addition, (c) component does not need to be contained in the dimer diamine composition.

In addition, when the ratio (b/c) of the area percent in the chromatograms of the components (b) and (c) is 1 or more, the molar ratio of the tetracarboxylic anhydride component and the diamine component (tetracarboxylic anhydride component/diamine component) is preferably Preferably, it is good to set it as 0.97 or more and less than 1.0, and control of the molecular weight of a polyimide becomes easier by setting it as such a molar ratio.

In addition, when the ratio (b/c) of the area percent of the chromatograms of the components (b) and (c) is less than 1, the molar ratio of the tetracarboxylic anhydride component and the diamine component (tetracarboxylic acid anhydride component/diamine component) is, Preferably, it is good to set it as 0.97 or more and 1.1 or less, and control of the molecular weight of a polyimide becomes easier by setting it as such a molar ratio.

It is preferable to refine|purify the dimer diamine composition used by this invention for the purpose of reducing components other than dimer diamine of (a) component. Although it does not restrict|limit especially as a purification method, Well-known methods, such as a distillation method and precipitation purification, are preferable. The dimerdiamine composition before purification can be obtained as a commercial item, for example, Croda Japan Co., Ltd. product PRIAMINE1073 (brand name), the same PRIAMINE1074 (brand name), the same PRIAMINE1075 (brand name) and the like.

As diamine compounds other than dimer diamine used for a DDA type|system|group thermoplastic polyimide, an aromatic diamine compound and an aliphatic diamine compound are mentioned. Specific examples thereof include 1,4-diaminobenzene (p-PDA; paraphenylenediamine), 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]sulfone, bis[4-(3-aminophenoxy)]biphenyl, bis[1-(3-aminophenoxy)]biphenyl, bis[ 4-(3-aminophenoxy)phenyl]methane, bis[4-(3-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)]benzophenone, 9,9-bis[4 -(3-aminophenoxy)phenyl]fluorene, 2,2-bis-[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis-[4-(3-aminophenoxy) C)phenyl]hexafluoropropane, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-methylenedi-o-toluidine, 4,4'-methylenedi-2,6- Xylidine, 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-methylethylidene)]bisaniline, 4,4'-[1,3-phenylene Bis(1-methylethylidene)]bisaniline, bis(p-aminocyclohexyl)methane, bis(p-β-amino-t-butylphenyl)ether, bis(p-β-methyl-δ-aminopentyl) ) Benzene, p-bis(2-methyl-4-aminopentyl)benzene, p-bis(1,1-dimethyl-5-aminopentyl)benzene, 1,5-diaminonaphthalene, 2,6-diaminonaphthalene , 2,4-bis(β-amino-t-butyl)toluene, 2,4-diaminotoluene, m-xylene-2,5-diamine, p-xylene-2,5-diamine, m-xylylene Diamine, p-xylylenediamine, 2,6-diaminopyridine, 2,5-diaminopyridine, 2,5-diamino-1,3,4-oxadiazole, piperazine, 2'-methoxy -4,4'-diaminobenzanilide, 4,4'-diaminobenzanilide, 1,3-bis[2-(4-aminophenyl)-2-propyl]benzene, 6-amino- and diamine compounds such as 2-(4-aminophenoxy)benzoxazole and 1,3-bis(3-aminophenoxy)benzene.

The DDA-based thermoplastic polyimide can be produced by reacting the above-described tetracarboxylic acid anhydride component with the diamine component in a solvent to produce polyamic acid and then heat-ring closure. For example, polyamic acid, which is a precursor of polyimide, is obtained by dissolving a tetracarboxylic anhydride component and a diamine component in an organic solvent in approximately equimolar amounts, stirring at a temperature within the range of 0 to 100° C. for 30 minutes to 24 hours, and performing polymerization reaction. In the reaction, the reactant components are dissolved in the organic solvent so that the resulting precursor is in the range of 5 to 50% by weight, preferably in the range of 10 to 40% by weight. Examples of the organic solvent used for the polymerization reaction include N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), N,N-diethylacetamide, and N-methyl-2-pi. Rollidone (NMP), 2-butanone, dimethyl sulfoxide (DMSO), hexamethylphosphoramide, N-methylcaprolactam, dimethyl sulfate, cyclohexanone, methylcyclohexane, dioxane, tetrahydrofuran, diglyme , triglyme, methanol, ethanol, benzyl alcohol, cresol, and the like. Two or more of these solvents may be used in combination, and an aromatic hydrocarbon such as xylene or toluene may be used in combination thereon. In addition, the amount of the organic solvent used is not particularly limited, but it is preferable to adjust the amount to be used so that the concentration of the polyamic acid solution obtained by the polymerization reaction is about 5 to 50 wt%.

The synthesized polyamic acid is usually advantageously used as a reaction solvent, but may be concentrated, diluted or substituted with another organic solvent if necessary. In addition, polyamic acids are generally used advantageously because of their excellent solvent solubility. The viscosity of the solution of polyamic acid is preferably in the range of 500 cps to 100,000 cps. If it is out of this range, defects such as thickness non-uniformity and streaks easily occur on the film during coating by a coater or the like.

The method of imidizing polyamic acid to form polyimide is not particularly limited, and for example, heat treatment of heating in the above solvent at a temperature within the range of 80 to 400° C. for 1 to 24 hours is suitably employed. do. In addition, the temperature may be heated under constant temperature conditions, or the temperature may be changed during the process.

In the DDA-based thermoplastic polyimide, by selecting the types of the tetracarboxylic acid anhydride component and the diamine component, or each molar ratio in the case of applying two or more types of tetracarboxylic acid anhydride component or diamine component, dielectric properties, coefficient of thermal expansion, and tensile modulus of elasticity , glass transition temperature, etc. can be controlled. Further, in the DDA-based thermoplastic polyimide, when a plurality of structural units of polyimide are provided, they may exist in blocks or at random, but they are preferably present at random.

The weight average molecular weight of the DDA-based thermoplastic polyimide is preferably in the range of, for example, 10,000 to 200,000, and if it is within this range, control of the weight average molecular weight of the polyimide becomes easy. Further, for example, when applied 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 applied as an adhesive for FPC, if the weight average molecular weight of the DDA-based thermoplastic polyimide is less than 20,000, 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 becomes insoluble in solvents, and defects such as uneven thickness and streaks of the adhesive layer during coating operation tend to occur. have.

The imide group concentration of the DDA-based thermoplastic polyimide is preferably 22 wt% or less, and more preferably 20 wt% or less. Here, "imide group concentration" means the value obtained by dividing the molecular weight of the imide group moiety (-(CO) ₂ —N-) in the polyimide by the molecular weight of the entire structure of the polyimide. When the imide group concentration exceeds 22% by weight, the molecular weight of the resin itself decreases, and the low hygroscopicity also deteriorates due to an increase in polar groups, and Tg and elastic modulus increase.

The most preferable DDA-based thermoplastic polyimide has a fully imidized structure. However, a part of polyimide may be made into amic acid. The imidization rate was determined by measuring the infrared absorption spectrum of the polyimide thin film by a single reflection ATR method using a Fourier transform infrared spectrophotometer (commercial product: FT/IR620 manufactured by JASCO Corporation), 1015 Based on the benzene ring absorber in the vicinity of cm ^-1 , it can be calculated from the absorbance of C=O stretching derived from the imide group at 1780 cm ^-1 .

<Crosslinking Formation>

(A) When the DDA-based thermoplastic polyimide in the component has a ketone group, an amino compound having the ketone group and at least two primary amino groups as functional groups (hereinafter referred to as “amino compound for crosslinking”) A crosslinked structure can be formed by reacting the amino group of ) to form a C═N bond. The heat resistance of the DDA-based thermoplastic polyimide can be improved by forming a cross-linked structure. As a preferable tetracarboxylic anhydride for forming a DDA-type thermoplastic polyimide having a ketone group, for example, 3,3',4,4'-benzophenonetetracarboxylic dianhydride (BTDA), and as a diamine compound, for example, and aromatic diamines such as 4,4'-bis(3-aminophenoxy)benzophenone (BABP) and 1,3-bis[4-(3-aminophenoxy)benzoyl]benzene (BABB).

For the purpose of forming a crosslinked structure, the resin composition of the present embodiment contains, in particular, BTDA residues derived from BTDA with respect to all tetracarboxylic acid residues, preferably 50 mol% or more, more preferably 60 mol% or more. (A) It is preferable to contain the DDA-type thermoplastic polyimide in a component, and the amino compound for crosslinking formation. In the present invention, "BTDA residue" means a tetravalent group derived from BTDA.

Examples of the amino compound for crosslinking include (I) dihydrazide compound, (II) aromatic diamine, (III) aliphatic amine, and the like. Among these, a dihydrazide compound is preferable. Aliphatic amines other than the dihydrazide compound easily form a crosslinked structure even at room temperature, and there is a concern about storage stability of the varnish. Thus, when a dihydrazide compound is used, the storage stability of a varnish and shortening of hardening time can be made compatible. As the dihydrazide compound, for example, oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, pimelic acid dihydrazide, suberic acid dihydrazide, and azelaic acid dihydrazide. Zide, sebacic acid dihydrazide, dodecane diacid dihydrazide, maleic acid dihydrazide, fumaric acid dihydrazide, diglycolic acid dihydrazide, tartrate dihydrazide, malic acid dihydrazide, phthalic acid dihydrazide, isophthalic acid dihydrazide Zide, terephthalic acid dihydrazide, 2,6-naphthoic acid dihydrazide, 4,4-bisbenzene dihydrazide, 1,4-naphthoic acid dihydrazide, 2,6-pyridine diacid dihydrazide, ita Dihydrazide compounds, such as conic acid dihydrazide, are preferable. The above dihydrazide compounds may be used individually or in mixture of 2 or more types.

In addition, amino compounds such as (I) dihydrazide compound, (II) aromatic diamine, and (III) aliphatic amine include, for example, a combination of (I) and (II), a combination of (I) and (III), Like the combination of (I), (II) and (III), it is also possible to use a combination of two or more types beyond categories.

In addition, from the viewpoint of making the network-like structure formed by crosslinking with the amino compound for crosslinking more compact, the amino compound for crosslinking used in the present invention has a molecular weight (weight when the amino compound for crosslinking is an oligomer). Average molecular weight) is preferably 5,000 or less, more preferably 90 to 2,000, still more preferably 100 to 1,500. Among these, the amino compound for crosslinking which has a molecular weight of 100-1,000 is especially preferable. When the molecular weight of the amino compound for crosslinking is less than 90, one amino group of the amino compound for crosslinking only forms a C = N bond with the ketone group of the DDA-based thermoplastic polyimide, and the periphery of the remaining amino groups becomes sterically bulky. Since it becomes large, the remaining amino group tends to be difficult to form a C=N bond.

When crosslinking the ketone group in the DDA-based thermoplastic polyimide in the component (A) and the amino compound for crosslinking, the amino compound for crosslinking is added to the resin solution containing the component (A), and The ketone group is subjected to a condensation reaction with the primary amino group of the amino compound for crosslinking. By this condensation reaction, the resin solution is cured to become a cured product. In this case, the addition amount of the amino compound for crosslinking is 0.004 to 1.5 moles, preferably 0.005 to 1.2 moles, more preferably 0.03 to 0.9 moles of primary amino groups in total with respect to 1 mole of the ketone group; Most preferably, it can be set as 0.04 mol to 0.6 mol. When the amount of the amino compound for crosslinking is less than 0.004 moles of primary amino groups in total with respect to 1 mole of ketone groups, the crosslinking by the amino compound for crosslinking is insufficient, so that heat resistance after curing tends to be difficult to be expressed, When the addition amount of the amino compound for crosslinking exceeds 1.5 mol, the unreacted amino compound for crosslinking acts as a thermoplastic and tends to decrease the heat resistance as an adhesive layer.

The conditions of the condensation reaction for crosslinking are: a ketone group in the DDA-based thermoplastic polyimide in component (A) reacts with a primary amino group of the amino compound for crosslinking to form an imine bond (C=N bond) If it is a condition, it will not restrict|limit in particular. The temperature of the heat condensation is set to release the water generated by the condensation to the outside of the system, or when the heat condensation reaction is continuously carried out after the synthesis of the DDA-based thermoplastic polyimide in the component (A). For simplification, etc., for example, in the range of 120-220 degreeC is preferable, and the inside of the range of 140-200 degreeC is more preferable. The reaction time is preferably about 30 minutes to 24 hours. The end point of the reaction is, for example, by measuring the infrared absorption spectrum using a Fourier transform infrared spectrophotometer (commercially available: FT/IR620 manufactured by Nippon Bunko Co., Ltd.), to a polyimide resin in the vicinity of 1670 cm ^-1 . It can be confirmed by the decrease or disappearance of the absorption peak derived from the ketone group in the present invention, and the appearance of the absorption peak derived from the imine group near 1635 cm ^-1 .

Heat condensation of the ketone group of the DDA-based thermoplastic polyimide in the component (A) and the primary amino group of the amino compound for crosslinking is, for example,

(1) A method of heating by adding an amino compound for crosslinking formation following the synthesis (imidization) of the DDA-based thermoplastic polyimide in the component (A);

(2) Prepare an excess amount of amino compound in advance as a diamine component, and continue to the synthesis (imidization) of the DDA-based thermoplastic polyimide in component (A), and the remainder not involved in imidation or amidation A method of heating together with a DDA-based thermoplastic polyimide using an amino compound as an amino compound for crosslinking;

or

(3) After processing the composition of the DDA-based thermoplastic polyimide in the component (A) to which the amino compound for crosslinking is added into a predetermined shape (for example, after coating on an arbitrary substrate or film) After forming into a phase), heating method,

etc. can be carried out.

Although it has been described that an imine bond is formed by the formation of a crosslinked structure for imparting heat resistance to the DDA-based thermoplastic polyimide in component (A), it is not limited thereto. For example, a compound having an unsaturated bond, such as an epoxy resin, an epoxy resin curing agent, maleimide, an activated ester resin, or a resin having a styrene skeleton may be blended and cured.

[(B) component]

The resin composition of this embodiment contains 1 or more types chosen from aromatic condensed phosphoric acid ester, a silica particle, or a liquid crystalline polymer filler as (B) component. Moreover, 2 or more types can also be used together as (B)component.

Hereinafter, the aromatic condensed phosphoric acid ester is described in order as "component (B1)", silica particles as "component (B2)", and liquid crystalline polymer filler as "component (B3)".

[(B1) component; aromatic condensed phosphoric acid ester]

(B1) "aromatic condensed phosphoric acid ester" of component is 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; It refers to a reaction product of a divalent phenol-based compound and phenol or alkylphenol. The dielectric properties can be improved by combining the aromatic condensed phosphoric acid ester with a polyimide obtained by using a dimerdiamine composition in a certain amount or more. Although the reason is not yet clear, due to the unique chemical structure of the aromatic condensed phosphate ester, the dielectric properties of the aromatic condensed phosphate ester and the compatibility with the polyimide obtained using the dimerdiamine composition are high, but the molecular chain mobility is excessive. Since it is not increased so much, it is estimated that 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 is excellent in stability.

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

[Formula 5]

In the general formula (3), a plurality of R's are each independently an aromatic hydrocarbon group which may have a substituent, Ar is a divalent organic group having an aromatic ring, and n means an integer of 1 or more. The aromatic condensed phosphate ester represented by the general formula (3) may be a multimer in which n is 2 or more other than the dimer in which n is 1. Moreover, it is not limited to a single compound, A mixture may be sufficient.

Examples of the aromatic hydrocarbon group which may have a substituent represented by R in the general formula (3) include an aryl group having 6 to 15 carbon atoms, and more specifically, a phenyl group, a methylphenyl group, a dimethylphenyl group, and a trimethylphenyl group. , an ethylphenyl group, a butylphenyl group, a nonylphenyl group, and the like.

Moreover, in General formula (3), as a preferable example of the divalent organic group represented by Ar, an alkylene group, an arylene group, etc. are mentioned, for example, These may be equipped with a substituent. As a more preferable thing, a phenylene group, group represented by following formula (4), etc. are mentioned, for example.

[Formula 6]

In Formula (4), Y ₁ is 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 the aromatic condensed phosphate ester include resorcinol bis-diphenyl phosphate, resorcinol bis-dixylenyl phosphate, and bisphenol A bis-diphenyl phosphate. Commercially available products are available as these aromatic condensed phosphate esters, for example, CR-733S (trade name), CR-741 (trade name), CR-747 (trade name), PX-200 (trade name), PX-200B (trade name) [Above, Daihachi Chemical Industry Co., Ltd. product] etc. are mentioned. You may use these aromatic condensed phosphoric acid ester in combination of 2 or more type.

<(B1) compounding quantity of component>

The weight ratio of the component (B1) to the component (A) in the resin composition of the present embodiment is within the range of 0.05 to 0.7, and considering film properties such as tensile modulus of elasticity when a resin film is formed, 0.2 to 0.5 It is preferable that it is within the range of (the same applies to the resin film mentioned later). If 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. (脆弱化) may occur. (B1) A dielectric characteristic can be improved by making the compounding quantity of a component into the said range. In addition, when (A) component is a polyamic acid, it converts into polyimide and shall compute weight ratio (it is the same hereafter).

Moreover, in the resin composition of this embodiment, (B1) component is mix|blended so that the weight ratio of the phosphorus derived from (B1) component with respect to the thermoplastic resin of (A) component may become in the range of 0.01-0.1. If the weight ratio of phosphorus derived from component (B1) is less than 0.01, the improvement of the dielectric properties is insufficient, and when it exceeds 0.1, the polyimide film (or polyimide layer) may become brittle.

(B1) component in the resin composition of this embodiment is the weight ratio of phosphorus derived from (B1) component with respect to the dimerdiamine composition contained in (A) component {phosphorus/(A) component derived from (B1) component) It is preferable that the dimerdiamine composition} in it exists in the range of 0.01-0.15. If it is less than the said lower limit, the improvement of a dielectric characteristic may become inadequate, and if it exceeds the said upper limit, formation of a polyimide may become difficult, and the brittleness of the polyimide film obtained may arise.

[(B2) component: silica particle]

Although either a crystalline silica particle and an amorphous silica particle can be used for the silica particle of (B2) component, It is preferable that the crystalline silica particle provided with a cristobalite crystal phase or a quartz crystal phase is included.

By mix|blending the silica particle of (B2) component, the dielectric loss tangent at the time of forming a resin film can be reduced. From the viewpoint of achieving a low dielectric loss tangent when the resin film is formed, it is particularly preferable to use silica particles having a cristobalite crystal phase as the crystalline silica particles. Silica particles having a cristobalite crystal phase have very excellent dielectric properties compared to general silica particles (for example, silica particles containing 90% by weight or more of a cristobalite crystal phase alone have a dielectric loss tangent of 0.0001 at 20 GHz) degree), so it can greatly contribute to the low dielectric loss tangent of the resin film.

Moreover, as a silica particle of (B2) component, it is preferable to use a spherical silica particle. The spherical silica particle is a silica particle whose shape is close to a true spherical shape, and the ratio of an average long diameter to an average minor diameter means 1 or a thing close to 1.

In addition, since silica is not thermally decomposed at a normal combustion temperature, flame retardancy can be improved by adding silica particles as component (B2).

In addition, from the viewpoint of achieving a low dielectric loss tangent when the resin film is formed, the total silica particles used are derived from SiO ₂ in the range of 2θ = 10° to 90° in the X-ray diffraction spectrum by CuKα ray. The ratio of the total area of the peaks derived from the cristobalite crystal phase and the quartz crystal phase to the total area of the total peaks is preferably 20% by weight or more, more preferably 40% by weight or more, and still more preferably 80% by weight or more. By increasing the ratio of the cristobalite crystal phase and/or the quartz crystal phase in the entire silica particle, it becomes possible to further reduce the dielectric loss tangent of the polyimide. If the ratio of the area of the peaks derived from the cristobalite crystal phase and the quartz crystal phase in the whole silica particle is less than 20 wt%, the effect of improving the dielectric properties becomes unclear. In addition, when the target peak in the X-ray diffraction spectrum is difficult to separate from the amorphous broad peak or overlaps with the peak of another crystalline phase, various known analysis methods, for example, the internal standard method Alternatively, the PONKCS method may be used.

The silica particles preferably have an average particle diameter D ₅₀ in the range of 6 to 20 µm, and more preferably in the range of 8 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 by the laser diffraction scattering method becomes 50%. When the average particle diameter D ₅₀ is within this range, the dielectric properties can be effectively improved, and the surface smoothness when a resin film is formed with the resin composition is not deteriorated, and a low-k film good in appearance can get When 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. When the average particle diameter D ₅₀ exceeds the above range, it may appear as irregularities on the surface of the resin film, which may deteriorate the smoothness of the film surface.

Moreover, it is preferable that 90 weight% or more of the silica particle with a particle diameter of 3 micrometers or more has a circularity of 0.7 or more, and it is more preferable that it is 0.9 or more. The circularity of silica particles can be obtained by image analysis, assuming a circle having the same projected area as the photographed particles, and the ratio of the circumference length of the circle to the circumference length of the particle. When the circularity is less than 0.7, the surface area increases, which may adversely affect the dielectric properties, and the viscosity increases when blended with the resin solution, making handling difficult. Moreover, also in the sphericity required three-dimensionally, a value substantially corresponding to the value of the said circularity is preferable.

Moreover, it is preferable that a true specific gravity of a silica particle is 2.3 or more. If the true specific gravity is less than 2.3, it is suggested that the crystallinity of the silica particles is small, and the effect of improving the dielectric properties is small.

The silica particle can select and use a commercial item suitably. For example, spherical cristobalite silica powder (NIPPON STEEL Chemical & Material, product name; CR10-20), spherical amorphous silica powder (Nitetsu Chemical & Materials Co., Ltd. product, brand name; SC70) -2) and the like can be preferably used. Moreover, you may use together 2 or more types of mutually different silica particles as a silica particle.

<(B2) compounding quantity of component>

The weight ratio of the component (B2) to the total of the component (A) and the component (B2) in the resin composition of the present embodiment is within the range of 5 to 60% by weight (the same applies to the resin film described later). If the weight ratio of the component (B2) to the total of the component (A) and the component (B2) is less than 5% by weight, the effect of improving dielectric properties and flame retardancy may become insufficient. Formation may become difficult, and also the resulting polyimide film may become brittle. (B2) By making the compounding quantity of a component into the said range, a dielectric characteristic and a flame retardance can be improved.

Moreover, when content of (B2) component exists in the range of 5 to 20 weight% with respect to the sum total of (A) component and (B2) component, 2θ = 10° to 90° of X-ray diffraction spectrum by CuKα ray It is preferable to mix the crystalline silica particles so that the total area of the peaks derived from the cristobalite crystal phase and the quartz crystal phase with respect to the total area of the total peaks derived from SiO ₂ in the range of is 40% by weight or more. On the other hand, when the content of component (B2) exceeds 20% by weight with respect to the total of component (A) and component (B2), crystalline silica particles so that the peak area derived from the cristobalite crystal phase and the quartz crystal phase is 30% by weight or more It is preferable to combine

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

[(B3) component: liquid crystalline polymer filler]

A liquid crystalline polymer filler is a particle|grain which consists of a liquid crystal polymer which forms the molten phase of optically anisotropy. The liquid crystal polymer forming the optically anisotropic melt phase is also called a thermotropic liquid crystal polymer. A polymer that forms a molten phase that forms optically anisotropy is a polymer that transmits polarized light when a sample in a molten state is observed under orthogonal nicol under a polarizing microscope equipped with a heating device. The liquid crystal polymer has almost no frequency dependence, has very excellent dielectric properties, and contributes to improvement of flame retardancy.

Although it does not specifically limit as a liquid crystal polymer, For example, well-known thermotropic liquid crystal polyester and polyesteramide derived from the compound classified into the following (1)-(4), and its derivative(s) are mentioned.

(1) aromatic or aliphatic dihydroxy compounds

(2) aromatic or aliphatic dicarboxylic acids

(3) aromatic hydroxycarboxylic acids

(4) aromatic diamines, aromatic hydroxylamines or aromatic aminocarboxylic acids

As the number of aromatic rings in the liquid crystal polymer increases, the effect of improving dielectric properties and flame retardancy can be expected. it is preferable

As a representative example of a liquid crystal polymer obtained from these raw material compounds, a copolymer comprising a combination of two or more selected from the structural units represented by the following formulas (a) to (g), the structural unit represented by the formula (a) or the formula ( A copolymer including any one of the structural units represented by b) is preferable, and a copolymer including the structural unit represented by the formula (a) and the structural unit represented by the formula (b) is more preferable. Formulas (a) and (b) are representative examples of structural units derived from aromatic hydroxycarboxylic acids, and Formulas (c), (d) and (e) are representative examples of structural units derived from aromatic dicarboxylic acids. and formulas (f) and (g) are representative examples of structural units derived from aromatic dihydroxy compounds (aromatic diols). Moreover, in the structural unit represented by Formula (a) - (g), the aromatic ring may be equipped with arbitrary substituents.

In particular, as a liquid crystal polymer with a low dielectric loss tangent,

A structural unit represented by formulas (a) and (b), a structural unit selected from formulas (c), (d) or (e), and a structure selected from formulas (f) or (g) liquid crystal polymers containing units in a specific ratio;

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 (g) in a specific ratio liquid crystal polymer comprising;

and the like.

[Formula 7]

In order to improve the dielectric properties of the resin film obtained from the resin composition, the liquid crystalline polymer filler is a single substance, and the 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. It is preferable to use one with a dielectric loss tangent in the range of preferably less than 0.0019, more preferably less than or equal to 0.0015 at 10 GHz.

Further, in the liquid crystalline polymer filler, when the dielectric loss tangent at 10 GHz of component (A) is Dfa, and the dielectric loss tangent at 10 GHz of component (B3) is Dfb, Dfb is less than 0.0019, and Dfa > Dfb is more preferable. .

Moreover, it is preferable as a liquid crystal polymer to contain an aromatic ring abundantly from a viewpoint of aiming at the improvement of a flame retardance. As the weight ratio of the aromatic ring in the liquid crystalline polymer filler, it is preferable to use 60% by weight or more, more preferably 70% by weight or more.

Further, as the liquid crystal polymer particles, it is preferable to use spherical liquid crystal polymer particles. The spherical liquid crystal polymer particles are liquid crystal polymer particles having a shape close to a true spherical shape, and the ratio of the average major diameter to the average minor diameter is 1 or close to 1.

The liquid crystal polymer particles preferably have an average particle diameter D ₅₀ in the range of 6 to 20 µm, and more preferably in the range of 8 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 by the laser diffraction scattering method becomes 50%. When the average particle diameter D ₅₀ is within this range, the smoothness of the surface when the resin film is formed with the resin composition is not deteriorated, and a low-k film with good appearance can be obtained. If the average particle diameter D ₅₀ is less than the above range, the liquid crystal polymer particles may agglomerate when blended as a resin composition, and a uniform resin composition may not be obtained. When the average particle diameter D ₅₀ exceeds the above range, it may appear as irregularities on the surface of the resin film, thereby deteriorating the smoothness of the film surface.

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

Liquid crystal polymer particles can be appropriately selected and used. For example, a low dielectric liquid crystalline polymer (manufactured by JXTG Energy Co., Ltd.) or the like can be preferably used. Further, as the liquid crystal polymer particles, two or more types of different liquid crystal polymer particles may be used in combination.

<(B3) compounding quantity of component>

The ratio of (B3) component with respect to the sum total of (A) component and (B3) component in the resin composition of this embodiment exists in the range of 15-50 volume%, It is in the range of 15-40 volume% It is preferable (the same applies to the resin film mentioned later). If the volume ratio of the component (B3) to the total of the component (A) and the component (B3) is less than 15% by volume, the effect of improving dielectric properties and flame retardancy may become insufficient. Formation may become difficult, and the resulting resin film may become brittle. (B3) By carrying out the compounding quantity of a component within the said range, a dielectric characteristic and a flame retardance can be improved. In addition, the volume ratio of (B3) component with respect to the total of (A) component and (B3) component is cross-sectional observation with a scanning electron microscope etc. with respect to the cured film, The ratio of the liquid crystalline polymer filler in the resin composition It can be calculated|required by the calculation method etc.

[Optional Ingredients]

The resin composition of this embodiment may contain an organic solvent. For example, a polyimide solution containing a solvent-soluble DDA-based thermoplastic polyimide and a solvent may be used. Examples of the organic solvent include N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), N,N-diethylacetamide, and N-methyl-2-pyrrolidone (NMP). , 2-butanone, dimethylsulfoxide (DMSO), hexamethylphosphoramide, N-methylcaprolactam, dimethyl sulfate, cyclohexanone, dioxane, tetrahydrofuran, diglyme, triglyme, cresol, etc. can Two or more of these solvents may be used in combination, and an aromatic hydrocarbon such as xylene or toluene may also be used in combination. Although there is no restriction|limiting in particular as content of an organic solvent, The density|concentration of a thermoplastic resin is adjusted to the usage-amount which becomes about 5 to 30 weight%, and it is preferable to use.

Moreover, the resin composition of this embodiment can contain a flame retardant, when using a liquid crystalline polymer filler as (B) component. Although there is no restriction|limiting in particular as a flame retardant, A phosphorus flame retardant is preferable. Since the aliphatic thermoplastic resin such as DDA-based thermoplastic polyimide has a low aromatic ring concentration, it cannot fully exhibit flame retardant properties even when a phosphorus-based flame retardant is added. Since the concentration is increased by the aromatic ring derived from the liquid crystal polymer, the formation of a char (carbonized film) during combustion is promoted and a high flame retardant effect is exhibited. From this point of view, when using the liquid crystalline polymer filler of component (B3), it is preferable to further add 15 to 30% by weight of a phosphorus-based flame retardant with respect to 100% by weight of the nonvolatile organic compound component of the resin composition. Here, the "nonvolatile organic compound component" means the remaining solid content after excluding the solvent and inorganic solid content from the resin composition. That is, the nonvolatile organic compound component contains the thermoplastic resin of component (A) and the liquid crystalline polymer filler of component (B3), and as optional components, resins other than thermoplastic resins, organic fillers other than liquid crystalline polymer fillers, plasticizers, It may contain a curing accelerator, a coupling agent, an organic pigment, an organic flame retardant other than a phosphorus flame retardant, and the like.

Examples of the phosphorus-based flame retardant include aromatic condensed phosphoric acid esters having the same structure as the component (B1), metal salts of organic phosphinic acids, and alkylphosphines (however, red phosphorus is excluded). These flame retardants may use together 2 or more types of compounds from which a type differs.

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

[Formula 8]

In the general formula (5), the two organic groups R ₁₁ and R ₁₂ are preferably the same or different from each other linear or branched C1-C6 alkyl group, phenyl group, or tolyl group. . In addition, in the general formula (5), the metal species M is selected from the group consisting of Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na and K. it is preferable Further, when the metal species M is a divalent or higher n-valent metal, M in the general formula (5) is changed to M1/n. In addition, in order to improve the flame retardant effect, it is preferable to increase the phosphorus content, specifically, the two organic groups R ₁₁ and R ₁₂ are preferably an alkyl group having 1 to 3 carbon atoms, and have flame retardancy and flexibility. In order to improve and suppress 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 are available, for example, Exolit OP930 (trade name), Exolit OP935 (trade name), Exolit OP935 (trade name), which are phosphinic acid aluminum salts manufactured by Clariant Japan. Lit OP940 (brand name) etc. are mentioned.

In the resin composition of the present embodiment, as optional components, other resin components other than the thermoplastic resin of component (A), crosslinking agents, inorganic fillers other than silica particles, organic fillers other than liquid crystal polymer fillers, plasticizers, and curing accelerators , a coupling agent, a pigment, etc. can be further mix|blended suitably. Examples of the crosslinking agent include amino compounds having at least two primary amino groups as functional groups (amino compounds for crosslinking formation), epoxy compounds, bismaleimide compounds, and acrylic (methacrylic) compounds. Examples of the inorganic filler include aluminum oxide, magnesium oxide, beryllium oxide, boron nitride, aluminum nitride, silicon nitride, aluminum fluoride, and calcium fluoride. These can be used 1 type or in mixture of 2 or more types.

[Viscosity]

The viscosity of the resin composition is a viscosity range in which it is easy to form a coating film of a uniform thickness by increasing handling (handleability / operability) when the resin composition is applied. It is more preferably within the range of 5000 cps to 50000 cps. If the viscosity is out of the above-mentioned range, defects such as thickness unevenness and streaks easily occur on the film during coating by a coater or the like.

[Preparation of resin composition]

The resin composition of this embodiment can be prepared, for example by creating the solution of (A) component using arbitrary solvents, adding (B) component there, and mixing uniformly.

For example, you may mix|blend (B) component directly into the resin solution of a DDA type|system|group thermoplastic polyimide. Moreover, you may mix|blend a part of (A) component simultaneously with (B) component, or after adding (B) component.

Either method may inject|throw-in whole quantity of (B) component at a time, and it may divide into several times and may add little by little. In addition, the raw materials may be put in a batch, or may be divided into several times and mixed little by little.

When the resin composition of this embodiment is used to form an adhesive layer, in addition to excellent flexibility and thermoplasticity, it has excellent dielectric properties and flame retardancy. For this reason, the resin composition of this embodiment is equipped with the characteristic suitable as an adhesive agent for coverlay films which protect wiring parts, such as an FPC and a rigid flex circuit board, 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), wherein the thermoplastic resin layer contains a solid content (residue excluding a solvent) of the resin composition as a main component. is made into a film. That is, while the resin film of this embodiment contains (A) component and (B) component, the weight ratio of (B) component with respect to (A) component is adjusted within a predetermined range similarly to the said resin composition. . Since the resin film of this embodiment has excellent high-frequency characteristics and flame retardancy in addition to flexibility and adhesiveness, for example, an adhesive layer for a coverlay film that protects wiring portions such as FPC, rigid flex circuit board, and the like; It can be preferably used for applications, such as a bonding sheet of a multilayer FPC.

The resin film of the present embodiment is not particularly limited as long as it is a film of an insulating resin including a thermoplastic resin layer formed of the above-described resin composition, and may be a film (sheet) made of an insulating resin, copper foil, glass plate, or polyimide. A film of an insulating resin laminated on a base material such as a resin sheet such as a mid-based film, a polyamide-based film, or a polyester-based film may be used.

<Glass Transition Temperature>

It is preferable that the glass transition temperature (Tg) of the resin film of this embodiment is 250 degrees C or less, and it is more preferable that it exists in the range of 40 degrees C or more and 200 degrees C or less. When the Tg of the resin film is 250° C. or less, thermocompression bonding at a low temperature is possible, so that internal stress generated during lamination can be relieved, and dimensional change after circuit processing can be suppressed. When the Tg of the resin film exceeds 250 DEG C, the bonding temperature becomes high and there is a risk of impairing the dimensional stability after circuit processing.

When (B1) component is used as (B) component, it is preferable that a resin film has the following physical properties.

<Genetic Characteristics>

(B) In the case of using the component (B1) as the component, the resin film has the following formula (i),

[Here, ε ₁ represents the relative dielectric constant at 10 GHz measured by a split post dielectric resonator (SPDR) after 24 hours of humidity control under a constant temperature and humidity condition (normal state) of 23° C. and 50% RH , Tanδ ₁ represents the dielectric loss tangent at 10 GHz measured by SPDR after 24 hours of humidity control under the conditions of constant temperature and humidity at 23° C. and 50% RH. In addition, "√ε ₁ " means the square root of ε ₁ ]

E ₁ value, which is an index indicating dielectric properties at 10 GHz after 24 hours of humidity control under constant temperature and humidity conditions of 23° C. and 50% RH, calculated based on The following is good. When the value of E ₁ exceeds the upper limit, disadvantages such as loss of electric signals on the transmission path of high-frequency signals are likely to occur when, for example, when used for circuit boards such as FPC.

<Relative permittivity>

In the case of using the component (B1) as the component (B), the resin film is, for example, at 23 ° C. , The relative dielectric constant (ε ₁ ) at 10 GHz after 24 hours of humidity control under the conditions of constant temperature and humidity of 50%RH is preferably 3.2 or less, and more preferably 3.0 or less. When the relative permittivity exceeds 3.2, for example, when used for circuit boards such as FPC, disadvantages such as loss of electric signals on the transmission path of high-frequency signals are likely to occur.

<Dielectric loss tangent>

In addition, in the case of using the component (B1) as the component (B), the resin film is, for example, a constant temperature and humidity at 23°C and 50%RH for reducing the loss of electrical signals when used in circuit boards such as FPC. The dielectric loss tangent (Tanδ ₁ ) at 10 GHz after 24 hours of humidity control under the condition of is preferably less than 0.005, more preferably less than 0.004. When this dielectric loss tangent is 0.005 or more, when it is used for circuit boards, such as an FPC, it becomes easy to generate|occur|produce disadvantages, such as an electrical signal loss, on the transmission path of a high frequency signal.

<Dependence on moisture absorption>

In the case of using the component (B1) as the component (B), the resin film is used for, for example, a circuit board such as an FPC, to reduce loss of electrical signals in dry and wet conditions and to ensure impedance matching. For, the following formula (ii),

[Here, ε ₂ represents the dielectric constant at 10 GHz measured by SPDR after absorption at 23° C. for 24 hours, and Tanδ ₂ represents the dielectric loss tangent at 10 GHz measured by SPDR after absorption at 23° C. for 24 hours. . In addition, "√ε ₂ " means the square root of ε ₂ ]

_In the E ₂ value, which is an index indicating the dielectric properties at 23° C. and 10 GHz after absorption for 24 hours, calculated based _{on the} /E ₁ ) is in the range of 3.0 to 1.0, preferably in the range of 2.5 to 1.0, more preferably in the range of 2.2 to 1.0. When E ₂ /E ₁ exceeds the upper limit, for example, when used in circuit boards such as FPC, the relative permittivity and dielectric loss tangent in wet conditions increase, resulting in loss of electrical signals in the transmission path of high-frequency signals, etc. disadvantages are more likely to occur.

<Moisture absorption rate>

In the case of using the component (B1) as the component (B), the resin film preferably has a moisture absorption rate in order to reduce the influence of humidity when used for circuit boards such as FPC. 0.5 weight% or less is good, More preferably, less than 0.3 weight% is good. Here, the "moisture absorption rate" means the moisture absorption rate after 24 hours or more has elapsed under the conditions of 23 degreeC and 50%RH constant temperature and humidity (it has the same meaning in this specification). When the moisture absorption of the resin film exceeds 0.5% by weight, for example, when used for circuit boards such as FPC, it is likely to be affected by humidity, and disadvantages such as fluctuations in the transmission speed of high-frequency signals are likely to occur. That is, if the moisture absorption of the resin film exceeds the above range, it is easy to absorb water with a high relative permittivity. it gets easier

<Storage modulus>

In the case of using the component (B1) as the component (B), the resin film may have a temperature range in which the storage elastic modulus sharply decreases in the range of 40 to 250°C with a rise in temperature. It is thought that the characteristic of such a resin film is a factor which relieves the internal stress at the time of thermocompression bonding, for example, and maintains dimensional stability after circuit processing. The resin film preferably has a storage modulus of 5×10 ⁷ [Pa] or less at the upper limit of the temperature range. By setting it as such a storage modulus, thermocompression bonding at 250 degrees C or less becomes possible even if it is the upper limit of the said temperature range, adhesiveness can be ensured and dimensional change after circuit processing can be suppressed. Moreover, since the resin film of this embodiment has high thermal expansibility but low elasticity, even if the coefficient of thermal expansion (CTE) exceeds 30 ppm/K, the internal stress generated during lamination can be relieved.

When (B2) component is used as (B) component, it is preferable that a resin film has the following physical properties.

<Relative permittivity>

When the component (B2) is used as the component (B), the resin film is used, for example, in order to ensure impedance matching when used in circuit boards such as FPC, and to reduce loss of electrical signals 23 The relative permittivity at 20 GHz after 24 hours of humidity control under constant temperature and humidity conditions of °C and 50%RH is preferably 3.2 or less, and more preferably 3.0 or less. When the relative permittivity exceeds 3.2, for example, when used for circuit boards such as FPC, disadvantages such as loss of electric signals on the transmission path of high-frequency signals are likely to occur.

<Dielectric loss tangent>

In addition, in the case of using the component (B2) as the component (B), the resin film is, for example, a constant temperature and humidity at 23°C and 50%RH for reducing the loss of electrical signals when used in circuit boards such as FPC. The dielectric loss tangent at 20 GHz after humidity control for 24 hours under the condition of is preferably less than 0.005, more preferably 0.004 or less, and most preferably 0.002 or less. When this dielectric loss tangent is 0.005 or more, when it is used for circuit boards, such as an FPC, it becomes easy to generate|occur|produce disadvantages, such as an electrical signal loss, on the transmission path of a high frequency signal.

When (B3) component is used as (B) component, it is preferable that a resin film has the following physical properties.

<Relative permittivity>

In the case of using the component (B3) as the component (B), the resin film is, for example, at 23° C., 50 Under the condition of constant temperature and humidity of %RH, the relative permittivity at 20 GHz after humidity control for 24 hours is preferably 3.2 or less, and more preferably 3.0 or less. When the relative permittivity exceeds 3.2, when used for a circuit board such as an FPC, disadvantages such as loss of electrical signals on the transmission path of high-frequency signals are likely to occur.

<Dielectric loss tangent>

In addition, in the case of using the component (B3) as the component (B), the resin film is, for example, a constant temperature and humidity at 23°C and 50%RH for reducing the loss of electrical signals when used in circuit boards such as FPC. The dielectric loss tangent at 20 GHz after humidity control for 24 hours under the condition of is preferably less than 0.005, more preferably 0.004 or less, and most preferably 0.002 or less. When this dielectric loss tangent is 0.005 or more, when it is used for circuit boards, such as an FPC, it becomes easy to generate|occur|produce disadvantages, such as an electrical signal loss, on the transmission path of a high frequency signal.

<thickness>

When the component (B1) is used as the component (B), the thickness of the resin film is, for example, 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. . If the thickness of the resin film is less than 5 μm, there is a risk of defects such as wrinkles occurring during conveyance in the manufacture of the resin film, etc. there is

Further, when using the component (B2) or component (B3) as the component (B), the thickness of the resin film is, for example, preferably within the range of 15 to 100 µm, and more preferably within the range of 20 to 50 µm. desirable. If the thickness of the resin film is less than 15 μm, there is a risk of defects such as wrinkles occurring during conveyance in the production of the resin film, etc. there is

In addition, when the thickness of the resin film is within the range of 15 µm to 20 µm, in order to suppress the unevenness of the surface of the resin film and maintain the smoothness of the film surface, silica particles of component (B2) or liquid crystal of component (B3) As the polymer filler, it is preferable to use one having an average particle diameter D ₅₀ in the range of 9 to 12 µm.

[Laminate]

A laminate according to one embodiment of the present invention includes a substrate and an adhesive layer laminated on at least one surface of the substrate, and the adhesive layer is made of the resin film. In addition, the laminated body may contain arbitrary layers other than the above. As a base material in a laminated body, base materials of inorganic materials, such as copper foil and a glass plate, and base materials of resin materials, such as a polyimide-type film, a polyamide-type film, and a polyester film, are mentioned, for example.

As a preferable aspect of a laminated body, a coverlay film, resin containing copper foil, etc. are mentioned.

[Coverlay Film]

A coverlay film, which is one form of a laminate, includes a film material layer for coverlay as a base material, and an adhesive layer laminated on one side of the film material layer for coverlay, and the adhesive layer is made of the resin film . Moreover, the coverlay film may contain the arbitrary layers other than the above.

Although the material of the film material layer for a coverlay is not specifically limited, For example, polyimide-type films, such as polyimide, polyetherimide, and polyamideimide, a polyamide-type film, a polyester-type film, etc. can be used. Among these, it is preferable to use a polyimide-based film having excellent heat resistance. In addition, the film material for coverlay may contain a black pigment in order to effectively express light-shielding properties, hiding properties, design properties, etc. It may contain optional ingredients such as removal pigments.

Although the thickness of the film material layer for coverlays is not specifically limited, For example, the inside of the range of 5 micrometers or more and 100 micrometers or less is preferable.

Moreover, although the thickness of an adhesive bond layer is not specifically limited, For example, the inside of the range of 10 micrometers or more and 75 micrometers or less is preferable.

The coverlay film of this embodiment can be manufactured by the method illustrated below.

First, as a first method, a varnish-like resin composition containing a solvent is applied to one side of the film material layer for a coverlay, and then dried at a temperature of, for example, 80 to 180° C. to form an adhesive layer. A coverlay film having a film material layer and an adhesive layer can be formed.

Further, as a second method, an adhesive film for an adhesive layer is formed by coating a varnish-like resin composition containing a solvent on an arbitrary substrate and peeling it after drying at a temperature of, for example, 80 to 180°C, and this adhesive A coverlay film can be formed by thermocompression-bonding a film with the film material layer for coverlays, for example at the temperature of 60-220 degreeC.

[Copper foil containing resin]

The resin-containing copper foil, which is another form of the laminate, is one in which an adhesive layer is laminated on at least one side of the copper foil as a substrate, and the adhesive layer is made of the resin film. Moreover, the resin containing copper foil of this embodiment may contain the arbitrary layers other than the above.

It is preferable to exist in the range of 2-125 micrometers, for example, and, as for the thickness of the adhesive bond layer in resin containing copper foil, the inside of the range of 2-100 micrometers is more preferable. If the thickness of the adhesive layer does not reach the lower limit, there are cases in which problems such as sufficient adhesiveness cannot be ensured may occur. On the other hand, when the thickness of the adhesive layer exceeds the upper limit, defects such as a decrease in dimensional stability occur. Further, from the viewpoint of lowering the dielectric constant and lowering the dielectric loss tangent, it is preferable that the thickness of the adhesive layer be 3 µm or more.

It is preferable that the material of the copper foil in resin containing copper foil has copper or a copper alloy as a main component. The thickness of copper foil becomes like this. Preferably it is 35 micrometers or less, More preferably, it is good in the range of 5-25 micrometers. It is preferable that the lower limit of the thickness of copper foil shall be 5 micrometers from a viewpoint of production stability and handling property. Further, the copper foil may be a rolled copper foil or an electrodeposited copper foil. Moreover, as copper foil, commercially available copper foil can be used.

The resin-containing copper foil may be prepared, for example, by sputtering a metal on a resin film to form a seed layer, and then forming a copper layer by, for example, copper plating, or by heating the resin film and copper foil. You may prepare by laminating by methods, such as crimping|compression-bonding. In addition, in order to form an adhesive bond layer on copper foil, resin containing copper foil may cast and dry the coating liquid of a resin composition, and after drying it to make a coating film, you may perform necessary heat processing and may prepare it.

[Metal clad laminate]

(Form 1)

A metal clad laminate 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 of the insulating resin layers is made of the resin film. In addition, the metal foil laminated board of this embodiment may contain arbitrary layers other than the above.

(Second form)

A metal clad laminate according to another embodiment of the present invention includes, for example, an insulating resin layer, an adhesive layer laminated on at least one surface of the insulating resin layer, and a metal layer laminated on the insulating resin layer with the adhesive layer interposed therebetween. A so-called three-layer metal clad laminate comprising a, wherein the adhesive layer is made of the resin film. In addition, the three-layer metal clad laminate may contain any layer other than the above. In the three-layer metal clad laminate, the adhesive layer may be formed on one or both sides of the insulating resin layer, and the metal layer may be formed on one or both sides of the insulating resin layer with the adhesive layer interposed therebetween. That is, the three-layer metal clad laminate may be a single-sided metal clad laminate or a double-sided metal clad laminate. A single-sided FPC or a double-sided FPC can be manufactured by performing wiring circuit processing in a method such as etching the metal layer of the three-layer metal clad laminate.

The insulating resin layer in the three-layer metal clad laminate is not particularly limited as long as it is made of an electrically insulating resin, for example, polyimide, epoxy resin, phenol resin, polyethylene, polypropylene, polytetrafluoroethylene, Although silicone, ETFE, etc. are mentioned, It is preferable that it is comprised from polyimide. The polyimide layer constituting the insulating resin layer may be a single layer or a plurality of layers, but it is preferable to include 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 to 125 mu m, more preferably in the range of 5 to 100 mu m. If the thickness of the insulating resin layer does not reach the lower limit, there may be problems such as not being able to guarantee sufficient electrical insulation. On the other hand, when the thickness of the insulating resin layer exceeds the upper limit, defects such as warpage of the three-layer metal clad laminate easily occur.

The thickness of the adhesive layer in the three-layer metal clad laminate is, for example, preferably in the range of 0.1 to 125 µm, more preferably in the range of 0.3 to 100 µm. In the three-layer metal clad laminate of the present embodiment, if the thickness of the adhesive layer does not reach the above lower limit, there are cases in which problems such as sufficient adhesiveness cannot be ensured may occur. On the other hand, when the thickness of the adhesive layer exceeds the upper limit, defects such as a decrease in dimensional stability occur. In addition, from the viewpoint of lowering the dielectric constant and lowering the dielectric loss tangent of the entire insulating layer, which is a laminate of the insulating resin layer and the adhesive layer, the thickness of the adhesive layer is preferably 3 µm or more.

Further, 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 within the range of 0.1 to 3.0, more preferably within the range of 0.15 to 2.0. By setting it as such a ratio, the curvature of a three-layer metal clad laminated board can be suppressed. Moreover, the insulating resin layer may contain a filler as needed. Examples of the filler include silicon dioxide, aluminum oxide, magnesium oxide, beryllium oxide, boron nitride, aluminum nitride, silicon nitride, aluminum fluoride, calcium fluoride, and metal salts of organic phosphinic acid. These can be used 1 type or in mixture of 2 or more types.

[circuit board]

A circuit board according to an embodiment of the present invention is formed by wiring the metal layer of the metal clad laminate according to any one of the above embodiments. Circuit boards, such as FPC, can be manufactured by processing one or more metal layers of a metal clad laminated board into pattern shape by a normal method, and forming a wiring layer (conductor circuit layer). Moreover, the circuit board may be equipped with the coverlay film which coat|covers the wiring layer.

(Example)

Examples of the present invention will be described in more detail below with reference to examples. However, the scope of the present invention is not limited to the examples. In addition, in the following examples, various measurements and evaluations are based on the following unless otherwise indicated.

[Method for measuring amine value]

About 2 g of dimerdiamine composition is weighed into a 200-250 mL Erlenmeyer flask, using phenolphthalein as an indicator, and 0.1 mol/L ethanolic potassium hydroxide solution is added dropwise until the solution shows a pale pink color. Then, it is dissolved in about 100 mL of neutralized butanol. 3 to 7 drops of a phenolphthalein solution is added thereto, and titration is performed with stirring with a 0.1 mol/L ethanolic potassium hydroxide solution until the sample solution turns pale pink. 5 drops of bromophenol blue solution are added thereto, and titrated with stirring with 0.2 mol/L hydrochloric acid/isopropanol solution until the sample solution turns yellow.

An amine titer is computed by following formula (1).

Amine number = {(V ₂ ×C ₂ )-(V ₁ ×C ₁ )}×M _KOH /m ...(1)

Here, the amine value is a value expressed in mgKOH/g, and M _KOH is the molecular weight of potassium hydroxide 56.1. In addition, V and C are the volume and concentration of the solution used for titration, respectively, and the subscripts 1 and 2 represent 0.1 mol/L ethanolic potassium hydroxide solution and 0.2 mol/L hydrochloric acid/isopropanol solution, respectively. Also, m is the weight of the sample in grams.

[Measurement of weight average molecular weight (Mw) of polyimide]

The weight average molecular weight was measured by a gel permeation chromatograph (HLC-8220GPC manufactured by Tosoh Corporation). Polystyrene was used as a standard material, and tetrahydrofuran (THF) was used as a developing solvent.

[Calculation of area percent of GPC and chromatogram]

In GPC, a 100 mg solution of a 20 mg dimerdiamine composition pretreated with 200 µL of acetic anhydride, 200 µL of pyridine and 2 mL of THF was diluted with 10 mL of THF (containing 1000 ppm of cyclohexanone), and the sample was prepared prepared. Tosoh Co., Ltd. product, brand name of the prepared sample; Measurements were made using HLC-8220GPC under the conditions of column: TSK-gel G2000HXL, G1000HXL, flow rate: 1 mL/min, column (oven) temperature: 40°C, injection amount: 50 µL. In addition, cyclohexanone was treated as a standard material for the correction of the runoff time.

At this time, the peak top of the main peak of cyclohexanone is adjusted so that the retention time is 27 minutes to 31 minutes, and the peak end is 2 minutes from the peak start of the main peak of cyclohexanone, and the peak of cyclohexanone is Each component (a) to (c);

(a) components appearing in the main peak;

(b) a component appearing in the GPC peak detected at a time slower than the minimum value on the time side of the slow retention time in the main peak as a reference;

(c) a component appearing in the GPC peak detected at a time earlier than the minimum value on the time side with the earliest retention time in the main peak as a reference;

was detected.

[Evaluation of genetic characteristics]

The polyimide film (polyimide film after curing) was subjected to temperature; 23°C, humidity; After standing for 24 hours under the condition of 50%, the relative permittivity (ε ₁ ) and the dielectric loss tangent (Tanδ ₁ ) at a frequency of 10 GHz were measured. Further, after absorption at 23° C. for 24 hours, the dielectric constant (ε ₂ ) and dielectric loss tangent (Tanδ ₂ ) of the polyimide film (polyimide film after curing) at a frequency of 10 GHz were measured.

[Measurement of moisture absorption]

Two test pieces (width 4 cm x length 25 cm) of a polyimide film were prepared, and were dried at 80 degreeC for 1 hour. Immediately after drying, it was placed in a constant temperature and humidity chamber at 23° C./50% RH, left still for 24 hours or more, and obtained from the weight change before and after that by the following formula.

Moisture absorption rate (wt%) = [(weight after moisture absorption - weight after drying)/weight after drying] × 100

[Measurement of absorption rate]

Two test pieces (width 4 cm x length 25 cm) of a polyimide film were prepared, and were dried at 80 degreeC for 1 hour. Immediately after drying, it was put into pure water at 23° C., left still for 24 hours or more, and obtained from the weight change before and after that by the following formula.

Water absorption (wt%) = [(weight after absorption - weight after drying)/weight after drying] × 100

[Glass transition temperature (Tg) and storage modulus]

The glass transition temperature (Tg) and storage modulus were measured from 30°C to 400°C using a dynamic viscoelasticity measuring device (DMA: UBM product, trade name; E4000F) for a polyimide film of 5 mm × 20 mm size. 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 modulus of elasticity (tanδ) becomes maximum was referred to as the glass transition temperature.

[Tensile Modulus]

The tensile modulus of elasticity is, using a tension tester (manufactured by ORIENTEC, trade name TENSILON), a tensile test is performed at 50 mm/min on a test piece having a width of 12.7 mm × a length of 127 mm, The tensile modulus at 25°C was obtained.

[Solder heat resistance test (dry)]

Circuit processing on polyimide copper clad laminate (Nitetsu Chemical & Materials Co., Ltd. product, product name: ESPANEX MB12-25-12UEG), wiring width / wiring spacing (L/S) = 1㎜/1㎜ A printed board on which the circuit of was formed was prepared. 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 this copper foil-attached test piece was dried at 105°C, it was immersed in a solder bath set at each evaluation temperature for 10 seconds, and the adhesion state was observed to determine the presence or absence of defects such as foaming, swelling, and peeling. Confirmed. Heat resistance was expressed as the upper limit temperature at which no defects occurred. For example, “320° C.” means that no defects were confirmed by evaluation in a 320° C. solder bath.

[Solder heat resistance test (moisture absorption)]

Circuit processing was performed on a polyimide copper clad laminate (Nitetsu Chemical & Materials Co., Ltd. product, trade name: Espanex MB12-25-12UEG) to produce a circuit with wiring width/interval (L/S) = 1 mm/1 mm. The formed printed board was prepared. 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. This copper foil-attached test piece was left to stand at 40°C and 80% relative humidity for 72 hours, then immersed in a solder bath set at each evaluation temperature for 10 seconds, and the adhesion state was observed, and defects such as foaming, swelling, and peeling were observed. The presence or absence of was confirmed. Heat resistance was expressed as the upper limit temperature at which no defects occurred, for example, “260° C.” means that no defects were confirmed by evaluation in a 260° C. solder bath.

[Measurement of Peel Strength]

Peel strength was measured using a Tensilon Tester (Toyo Seiki Seisaku-sho Co., Ltd. product, trade name; STROGRAPH VE-10), using a sample (substrate) having a width of 1 mm. / The resin layer side of the laminated body composed of a resin layer) was fixed to an aluminum plate with a double-sided tape, and the force at the time of peeling the resin layer and the base material at a speed of 50 mm/min in a 180 degree direction was calculated|required.

[Evaluation of warpage]

Polyimide film material with a thickness of 25 μm (DU PONT-TORAY Co., Ltd. product, trade name; Kapton 100EN) or on 12 μm copper foil so that the thickness after drying becomes 25 μm The mid solution was apply|coated and the test piece was produced. In this state, the polyimide film material or copper foil was placed so that it became the lower surface, the average of the heights of the four corners of the test piece were measured, and 5 mm or less was considered "good", and the case exceeding 5 mm was "impossible".

The abbreviation used in this Example shows the following compounds.

DDA1: Croda Japan Co., Ltd. product, trade name; Distilled and purified PRIAMINE1075 ((a) component; 98.2 wt%, (b) component: 0%, (c) component: 1.9%, amine value: 206 mgKOH/g)

DDA2: Croda Japan Co., Ltd. product, trade name; PRIAMINE1075 distilled and purified ((a) component; 99.2 wt%, (b) component: 0%, (c) component; 0.8%, amine value: 210 mgKOH/g)

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

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

N-12: dodecane diacid dihydrazide

NMP: N-methyl-2-pyrrolidone

PX-200: phosphate ester (product of Daihachi Chemical Industry Co., Ltd., trade name; PX-200, non-halogen aromatic condensed phosphate ester, phosphorus content; 9.0%)

PX-202: phosphate ester (product of Daihachi Chemical Industries, Ltd., trade name; PX-202, non-halogen aromatic condensed phosphate ester, phosphorus content; 8.1%)

SR-3000: Phosphoric acid ester (manufactured by Daihachi Chemical Industries, Ltd., trade name; SR-3000, non-halogen aromatic condensed phosphoric acid ester, phosphorus content; 7.0%)

DA-850: Phosphate ester (product of Daihachi Chemical Industry Co., Ltd., trade name; DAIGUARD-850, non-halogen aromatic condensed phosphate ester, phosphorus content; 16.0% or more)

TPP (product of Daihachi Chemical Industry Co., Ltd., trade name; TPP, non-halogenated phosphate ester, phosphorus content; 9.5%)

TCP (product of Daihachi Chemical Industry Co., Ltd., trade name; TCP, non-halogen phosphate ester, phosphorus content; 8.4%)

TXP (product of Daihachi Chemical Industry Co., Ltd., trade name; TXP, non-halogen phosphate ester, phosphorus content; 7.6%)

CR-733 (manufactured by Daihachi Chemical Industry Co., Ltd., trade name; CR-733S, non-halogen aromatic condensed phosphate ester, phosphorus content; 10.9%)

CR-741 (manufactured by Daihachi Chemical Industry Co., Ltd., trade name; CR-741, non-halogen aromatic condensed phosphate ester, phosphorus content; 8.9%)

CM-6R: Phosphorus-nitrogen compound (Daiwa Chemical Industries, product name; fran CM-6R, average particle diameter 5㎛)

MC-6000 (Nissan Chemical Corporation, trade name; MC-6000, non-halogen melamine cyanurate)

Filler 1: Nittetsu Chemical & Materials Co., Ltd. product, brand name; CR10-20 (spherical cristobalite silica powder, spherical, silica content; 99.4% by weight, cristobalite crystalline phase; 93% by weight, true specific gravity; 2.33, D ₅₀ ; 10.8 μm, D ₉₀ ; 16.4 μm, D ₁₀₀ ; 24.1 μm, 10 GHz Relative permittivity at; 3.16, dissipation loss tangent at 10 GHz; 0.0008)

Filler 2: Nittetsu Chemical & Materials Co., Ltd. product, trade name; SC70-2 (spherical amorphous silica powder, spherical, silica 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, Dielectric loss tangent at 10 GHz; 0.0015)

Flame retardant 1: Clariant Japan Co., Ltd. product, brand name; ExolitOP935 (Aluminum Alkyl Phosphate)

Flame retardant 2: Daihachi Chemical Industry Co., Ltd. product, trade name; SR-3000 (Condensed Phosphate Ester)

LCP filler: JXTG Energy Co., Ltd. product (low dielectric liquid crystalline polymer, particle size (D ₅₀ ); 9.6㎛, relative permittivity at 10GHz; 3.27, dielectric loss tangent at 10GHz; 0.0009)

In addition, in said DDA1 and DDA2, "%" of (b) component and (c)component means the area percent of the chromatogram in a GPC measurement. In addition, the molecular weights of DDA1 and DDA2 were computed by following formula (1).

Molecular weight = 56.1 x 2 x 1000 / amine value ... (1)

(Synthesis Example 1-1)

In a 1000 ml separable flask, 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 were put, and mixed well at 40 ° C. for 1 hour to prepare a polyamic acid solution. did The polyamic acid solution was heated to 190° C., heated and stirred for 10 hours, and imidized by adding 125 g of xylene. Polyimide solution 1-a (solid content concentration; 30% by weight, weight average molecular weight; 82,900, amine value; 206 mgKOH/g) was prepared.

(Synthesis Examples 1-2 to 1-3)

Polyimide solutions 1-b to 1-c were prepared in the same manner as in Synthesis Example 1-1 except for the raw material composition shown in Table 1-1.

[Table 1-1]

(Production Example 1-1)

In 169.49 g (50 g as solid content) of polyimide solution 1-a obtained in Synthesis Example 1-1, 2.7 g of N-12 (0.0105 mol; primary amino group is equivalent to 0.35 mol per 1 mol of ketone group in BTDA) was blended, diluted by adding 6.0 g of NMP, and further stirred for 1 hour to obtain polyimide solution 1-1a.

The obtained polyimide solution 1-1a was mixed with a release PET film (Higashiyama Film Co., Ltd. (HYNT) product, trade name; HY-S05, length × width × thickness = 200 mm × 300 mm × 25 μm) of The polyimide film 1-1a' with a thickness of 25 micrometers was prepared by apply|coating to one side, drying at 80 degreeC for 15 minutes, and peeling from the mold release PET film. This polyimide film 1-1a' was pressed under the conditions of a temperature of 160 degreeC, a pressure of 3.5 MPa, and time of 60 minutes, and the polyimide film 1-1a was obtained.

Various evaluation results of 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; 0.07%, water absorption; 0.6%, Tg; 54°C, 200°C storage modulus; 5.0×10 ⁶ Pa, tensile modulus; 0.7 GPa, solder heat resistance (dry); 280°C, solder heat resistance (moisture absorption); 260°C, Peel Strength; 1.0 kN/m or more

(Production Examples 1-2, 1-3)

In the same manner as in Production Example 1-1, except that polyimide solutions 1-b and 1-c were used in place of polyimide solution 1-a, polyimide solutions 1-1b, 1-1c and polyimide film 1- 1b and 1-1c were obtained.

Various evaluation results of polyimide films 1-1b and 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; 0.07%, water absorption; 0.2%, Tg; 54°C, 200°C storage modulus; Unmeasured, tensile modulus; 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; 0.17%, water absorption; 0.7%, Tg; 106°C, 200°C storage modulus; less than 1.0×10 ⁶ Pa, tensile modulus; 1.4 GPa

[Example 1-1]

With respect to the polyimide solution 1-1a (100 weight part as solid content) obtained by Production Example 1-1, 10 weight part of SR-3000 was mix|blended, and the polyimide composition 1-1 was obtained. The obtained polyimide composition 1-1 was apply|coated to the single side|surface of a mold release PET film, and it dried at 80 degreeC for 15 minutes, and peeled from the mold release PET film, polyimide film 1-1' with a thickness of 25 micrometers was prepared.

This polyimide film 1-1' was heated in oven at the temperature of 160 degreeC, and the conditions of 2 hours, and the polyimide film 1-1 was obtained.

Various evaluation results of polyimide film 1-1 are as follows.

relative permittivity (ε ₁ ); 2.6, dielectric loss tangent (Tanδ ₁ ); 0.0022

[Examples 1-2 to 1-16]

Each component was mix|blended in the ratio (part by weight) shown in Table 1-2, and it carried out similarly to Example 1-1, and obtained polyimide compositions 1-2-1-16. In addition, in Table 1-2, "DDA composition" means a dimerdiamine composition (it is the same also in Table 1-3).

[Table 1-2]

Using the obtained polyimide compositions 1-2 to 1-16, in the same manner as in Example 1-1, polyimide films 1-2 to 1-16 were prepared.

Various evaluation results of polyimide films 1-2 to 1-16 are as follows.

<Polyimide film 1-2>

relative permittivity (ε ₁ ); 2.7, dielectric loss tangent (Tanδ ₁ ); 0.0022, tensile modulus; 0.7 GPa, Peel Strength; 1.4 kN/m

<Polyimide 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, absorption rate; 0.1%, Tg; 54°C, tensile modulus; 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 modulus; 0.5 GPa, Peel Strength; 1.5 kN/m

<Polyimide Film 1-5>

relative permittivity (ε ₁ ); 2.6, dielectric loss tangent (Tanδ ₁ ); 0.0022, tensile modulus; 0.7 GPa

<Polyimide Film 1-6>

relative permittivity (ε ₁ ); 2.7, dielectric loss tangent (Tanδ ₁ ); 0.0023, tensile modulus; 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, absorption rate; 0.29%, tensile modulus; 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, absorption rate; 0.54%, tensile modulus; 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, absorption rate; 0.91%, tensile modulus; 0.3 GPa, Peel Strength; 1.4 kN/m

<Polyimide Film 1-10>

relative permittivity (ε ₁ ); 2.7, dielectric 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 Examples 1-1 to 1-18]

Each component was blended in the proportions (parts by weight) shown in Table 1-3, and in the same manner as in Example 1-1, polyimide compositions 1-17 to 1-34 were obtained.

[Table 1-3]

Using the obtained polyimide compositions 1-17 to 1-34, polyimide films 1-17 to 1-34 were prepared in the same manner as in Example 1-1.

Various evaluation results of the polyimide films 1-17 to 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, absorption rate; 0.2%, tensile modulus; 0.9 GPa, Peel Strength; 1.2 kN/m

<Polyimide Film 1-18>

relative permittivity (ε ₁ ); 2.9, dielectric loss tangent (Tanδ ₁ ); 0.0025, tensile modulus; 0.6 GPa, Peel Strength; 0.4 kN/m

<Polyimide Film 1-19>

relative permittivity (ε ₁ ); 2.6, dielectric loss tangent (Tanδ ₁ ); 0.0031, tensile modulus; 0.3 GPa

<Polyimide Film 1-20>

relative permittivity (ε ₁ ); 2.8, dielectric loss tangent (Tanδ ₁ ); 0.0041, tensile modulus; 0.1 GPa

<Polyimide Film 1-21>

relative permittivity (ε ₁ ); 2.6, dielectric loss tangent (Tanδ ₁ ); 0.0028, tensile modulus; 0.2 GPa

<Polyimide Film 1-22>

relative permittivity (ε ₁ ); 2.8, dielectric loss tangent (Tanδ ₁ ); 0.0033, tensile modulus; 0.0GPa

<Polyimide Film 1-23>

relative permittivity (ε ₁ ); 2.7, dielectric loss tangent (Tanδ ₁ ); 0.0026, tensile modulus; 0.3 GPa

<Polyimide Film 1-24>

relative permittivity (ε ₁ ); 2.8, dielectric loss tangent (Tanδ ₁ ); 0.0028, tensile modulus; 0.0GPa

<Polyimide Film 1-25>

relative permittivity (ε ₁ ); 2.7, dielectric loss tangent (Tanδ ₁ ); 0.0028, tensile modulus; 0.3 GPa

<Polyimide Film 1-26>

relative permittivity (ε ₁ ); 2.7, dielectric loss tangent (Tanδ ₁ ); 0.0034, tensile modulus; 0.1 GPa

<Polyimide Film 1-27>

relative permittivity (ε ₁ ); 2.7, dielectric loss tangent (Tanδ ₁ ); 0.0027, tensile modulus; 0.4 GPa

<Polyimide Film 1-28>

relative permittivity (ε ₁ ); 2.7, dielectric loss tangent (Tanδ ₁ ); 0.0031, tensile modulus; 0.2 GPa

<Polyimide Film 1-29>

relative permittivity (ε ₁ ); 2.7, dielectric loss 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 1-34>

relative permittivity (ε ₁ ); 2.6, dielectric loss tangent (Tanδ ₁ ); 0.0021

The above results are put together, and the evaluation results of the dielectric properties of the polyimide films 1-1 to 1-34 are shown in Tables 1-4 and 1-5.

[Table 1-4]

[Table 1-5]

[Example 1-17]

Each component was blended in the proportions (parts by weight) shown in Table 1-2, and the polyimide composition 1-2 prepared in the same manner as in Example 1-1 was prepared as a polyimide film material P1 (manufactured by Toray DuPont Co., Ltd.). , trade name: Kapton 50EN, relative permittivity at 10 GHz frequency = 3.6, dielectric loss tangent at frequency 10 GHz = 0.0084, length × width × thickness = 200 mm × 300 mm × 12 μm) applied on one side, and at 80 ° C for 15 minutes It dried and obtained the coverlay film 1-17 whose thickness of an adhesive bond layer is 25 micrometers. The state of the curvature of the obtained coverlay film 1-17 was "good|favorableness".

[Example 1-18]

The release PET film was laminated so as to be in contact with the adhesive layer side of the coverlay films 1-17, and the temperature was 160° C., the pressure was 0.8 MPa, and the pressure was pressed using a vacuum laminator for 2 minutes. Thereafter, the polyimide composition 1-2 was applied to the polyimide film material P1 side of the coverlay film 1-17 of the coverlay film 1-17 in which the release PET film was compressed so that the thickness after drying was 25 µm, and dried at 80°C for 15 minutes. Then, the polyimide composition 1-2 was applied and laminated so that the release PET film was in contact with the dried side, and the temperature was 160 ° C., the pressure was 0.8 MPa, and 2 minutes was pressed using a vacuum laminator, and the adhesive on both sides of the polyimide film material P1. A laminated body 1-18 provided with a layer was obtained.

[Example 1-19]

The polyimide composition 1-2 was applied to one side of an electrodeposited copper foil having a thickness of 12 µm and dried at 80°C for 15 minutes to obtain a resin-containing copper foil 1-19 having an adhesive layer having a thickness of 25 µm. The state of the curvature of the obtained resin containing copper foil 1-19 was "good|favorableness".

[Example 1-20]

Polyimide composition 1-2 was applied to one side of an electrodeposited copper foil having a thickness of 12 µm, and dried at 80°C for 30 minutes to obtain a resin-containing copper foil 1-20 having an adhesive layer having a thickness of 50 µm. The state of the curvature of the obtained resin containing copper foil 1-20 was "good|favorableness".

[Example 1-21]

Polyimide composition 1-2 was applied again to the surface of the adhesive layer of the resin-containing copper foil 1-19, and dried at 80° C. for 30 minutes to obtain a resin-containing copper foil 1-21 having a total thickness of the adhesive layer of 100 μm. got it The state of the curvature of the obtained resin containing copper foil 1-21 was "good|favorableness".

[Example 1-22]

Polyimide composition 1-2 was apply|coated to the single side|surface of a mold release PET film, and the 50 micrometers thickness polyimide film 1-35 was obtained by peeling from the mold release PET film by drying at 80 degreeC for 30 minutes.

[Example 1-23]

On an electrodeposited copper foil having a thickness of 12 µm, polyimide film 1-2, polyimide film material P2 (manufactured by Toray DuPont Co., Ltd., trade name; Kapton 100-EN, thickness 25 µm, dielectric constant at a frequency of 10 GHz = 3.6, frequency Dielectric loss tangent at 10 GHz = 0.0084), polyimide film 1-2 and an electrodeposited copper foil having a thickness of 12 μm are sequentially laminated, and after pressing at a temperature of 160° C., a pressure of 0.8 MPa, and 2 minutes using a vacuum laminator, the temperature is 160° C. The temperature was raised to , and heat treatment was performed at 160° C. for 4 hours to obtain a copper clad laminate 1-23.

[Example 1-24]

On an electrodeposited copper foil having a thickness of 12 µm, the coverlay film 1-17 is laminated so that the adhesive layer side of the coverlay film 1-17 is in contact with the copper foil, and is pressed using a vacuum laminator at a temperature of 160°C, a pressure of 0.8 MPa, and 2 minutes, and then the temperature is raised from room temperature to 160°C. and heat-treated at 160° C. for 2 hours to obtain a copper clad laminate 1-24.

[Example 1-25]

A polyimide film 1-2 is laminated on a rolled copper foil having a thickness of 12 mu m, and the polyimide film material P1 side of the coverlay film 1-17 is laminated so that the polyimide film 1-2 is in contact with the coverlay film 1 - 17, a rolled copper foil having a thickness of 12 μm was sequentially laminated on the adhesive layer side, and after pressing at a temperature of 160° C., a pressure of 0.8 MPa, and 2 minutes using a vacuum laminator, the temperature was raised from room temperature to 160° C. and heat treatment was performed at 160° C. for 2 hours. , copper clad laminates 1-25 were obtained.

[Example 1-26]

Prepare two resin-containing copper foils 1-19, and on the adhesive layer side of the two resin-containing copper foils 1-19, polyimide film material P3 (manufactured by Toray DuPont, trade name; Kapton 200-EN, thickness 50 µm, The dielectric constant at a frequency of 10 GHz = 3.6, the dielectric loss tangent at a frequency of 10 GHz = 0.0084) are laminated so that they are in contact, and after pressing at a temperature of 160 ° C, a pressure of 0.8 MPa and 5 minutes using a vacuum laminator, the temperature is raised from room temperature to 160 ° C. It was heat-treated at 160 degreeC for 4 hours, and copper clad laminated board 1-26 was obtained.

[Example 1-27]

Polyimide composition 1-2 is a resin layer of single-sided copper clad laminate M1 (manufactured by Nittetsu Chemical & Materials, trade name; Espanex MC12-25-00UEM, length × width × thickness = 200 mm × 300 mm × 25 μm) It applied to the side surface and dried at 80 degreeC for 30 minutes, and the adhesive agent addition copper clad laminated board 1-27 whose thickness of an adhesive bond layer is 50 micrometers was obtained. The adhesive layer was laminated on the adhesive layer side of the copper clad laminate 1-27 with an adhesive so that the resin layer side of the single-sided copper clad laminate M1 was in contact with the copper clad laminate 1 -27 was obtained.

[Example 1-28]

The polyimide film 1-2 is laminated on the resin layer side of the single-sided copper clad laminate M1, and the resin layer side of the single-sided copper clad laminate M1 is laminated on it so that the polyimide film 1-2 is in contact with it, and the temperature using a small precision press machine is used. It was crimped|bonded at 160 degreeC, the pressure of 4.0 MPa, and 120 minutes, and copper clad laminated board 1-28 was obtained.

[Example 1-29]

The polyimide composition 1-2 was apply|coated to the single side|surface of the mold release PET film, and the adhesive layer was peeled from the mold release PET film by drying at 80 degreeC for 15 minutes, and the polyimide film 1-36 with a thickness of 15 micrometers was obtained.

[Example 1-30]

A double-sided copper clad laminate M2 (manufactured by Nittetsu Chemical & Materials Co., Ltd., trade name; Espanex MB12-25-00UEG) was prepared, and the copper foil on one side was subjected to circuit processing by etching to form a conductor circuit layer. A wiring board 1-1A was obtained.

The copper foil on one side of the double-sided copper clad laminate M2 was removed by etching to obtain a copper clad laminate 1-1B.

In a state where the polyimide film 1-2 was sandwiched between the surface of the wiring board 1-1A on the conductor circuit layer side and the surface of the copper clad laminate 1-1B on the resin layer side, the temperature was 160°C and the pressure was 4.0 MPa, for 120 minutes. By thermocompression bonding, multilayer circuit boards 1-30 were obtained.

[Example 1-31]

Liquid crystal polymer film (Kuraray Co., Ltd. product, trade name; CT-Z, thickness; 50㎛, CTE; 18ppm/K, thermal deformation temperature; 300℃, relative permittivity at 10GHz frequency = 3.40, frequency at 10GHz (dielectric loss tangent = 0.0022) as an insulating substrate, a copper clad laminate 1-1C having an electrodeposited copper foil with a thickness of 18 μm on both sides was prepared, and circuit processing was performed on one side of the copper foil by etching to form a conductor circuit layer The formed wiring board 1-1C was obtained.

The copper foil on one side of the copper-clad laminate 1-1C was removed by etching to obtain a copper-clad laminate 1-1D.

In a state where the polyimide film 1-2 was sandwiched between the surface of the wiring board 1-1C on the conductor circuit layer side and the copper clad laminate 1-1D surface on the insulating base layer side, the temperature was 160°C, the pressure was 4.0 MPa, and for 120 minutes. A multilayer circuit board 1-31 was obtained by thermocompression bonding.

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

[Evaluation of genetic characteristics]

<Silica Particles>

Using the vector network analyzer (Keysight Technologies product, trade name; Vector Network Analyzer E8363C) and the relative permittivity measuring device of KANTO Electronic Application and Development Co., Ltd. product by cavity resonator perturbation method , relative permittivity measurement mode; TM020 was set to measure the relative permittivity and dielectric loss tangent of silica particles at a frequency of 10 GHz. In addition, silica particles were measured by filling a sample tube tube (inner diameter 1.68 mm, outer diameter 2.28 mm, height 8 cm) as a powdery form.

<Resin Film>

Using a Vector Network Analyzer (manufactured by Keysight Technologies, trade name; Vector Network Analyzer E8363C) and a split post dielectric resonator (SPDR), 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 subjected to temperature; 23°C, humidity; After allowing to stand for 24 hours under the condition of 50%, the relative permittivity and dielectric loss tangent at a frequency of 20 GHz were measured.

[Measurement of particle diameter]

Particle diameter by laser diffraction/scattering measurement method using a laser diffraction particle size distribution measuring device (Malvern product, trade name; Master Sizer3000), water as a dispersion medium, and a particle refractive index of 1.54 was measured.

[Measurement of true specific gravity]

Using a continuous automatic powder true density measuring device (Seishin Enterprise Co., Ltd. product, trade name; AUTO TRUE DENSER MAT-7000), the pycnometer method (liquid phase displacement method) ) was measured for true specific gravity.

[Measurement of cristobalite crystal phase]

All diffraction patterns (peak positions _, peak positions, From the peak width and peak intensity), the total area of all peaks derived from SiO ₂ is calculated. Next, the peak position derived from the cristobalite crystal phase was specified, the total area of all peaks of the cristobalite crystal phase was calculated, and the ratio (weight%) to the total area of all peaks derived from SiO ₂ was calculated. In addition, the attribution of each peak referred to the database of the International Center for Diffraction Data (ICDD).

[Measurement of tensile modulus and maximum elongation]

Using a tension tester (Tensilon manufactured by Orientec Co., Ltd.), a tensile test of 50 mm/min was performed on the specimen (width: 12.7 mm, length; 127 mm), and tensile modulus of elasticity and maximum elongation at 25°C figure was saved.

[Measurement of glass transition temperature (Tg)]

temperature; 160°C, pressure; 3.5 MPa, time; The adhesive sheet pressed under the conditions for 60 minutes was cut into a 5 mm × 20 mm size test piece, and from 30° C. to 300° C. using a dynamic viscoelasticity measuring device (DMA: UBM product, trade name; E4000F). Measurement was performed at a temperature increase rate of 4°C/min and a frequency of 11 Hz, and the temperature at which the change in elastic modulus (tan δ) becomes the maximum was set as the glass transition temperature.

[Evaluation of film retention properties]

Film retention was evaluated by the following procedure. The adhesive sheet was cut out into a test piece having a width of 20 mm and a length of 20 mm, and after folding so that folds were formed along a diagonal line, it was returned to its original state and the state of the film was observed. At this time, the thing which did not crack in the test piece even after folding and unfolding was set as "good", and the thing which cracked even in a part was set as "impossible".

[Solder heat resistance test (dry)]

Copper foil on one side of the double-sided copper clad laminate (Nittetsu Chemical & Materials Co., Ltd. product, trade name; Espanex MB12-25-12UEG) is removed by etching, and the copper foil on the other side is circuit-processed, A printed board on which a circuit of L/S) = 1 mm/1 mm was formed was prepared. An adhesive sheet is placed on the wiring of the printed board, and a polyimide film (manufactured by Toray DuPont Co., Ltd., trade name; Kapton 50EN-S) is laminated on the opposite side of the side where the adhesive sheet is in contact with the printed board. ; 160°C, pressure; 3.5 MPa, time; Pressing was performed under the conditions for 60 minutes. After the copper foil-attached test piece was dried at 105° C., it was immersed in a solder bath set at each evaluation temperature for 10 seconds, and the adhesion state was observed to confirm the presence or absence of defects such as foaming, swelling, and peeling. Heat resistance was expressed as the upper limit temperature at which no defects occurred. For example, “320° C.” means that no defects were confirmed by evaluation in a 320° C. solder bath.

[Solder heat resistance test (moisture absorption)]

Copper foil on one side of a double-sided copper clad laminate (Nittetsu Chemical & Materials Co., Ltd. product, trade name; Espanex MB12-25-12UEG) is removed by etching, and the copper foil on the other side is circuit-processed, and the wiring width / wiring spacing (L /S) = 1mm/1mm A printed circuit board was prepared. An adhesive sheet is placed on the wiring of the printed board, and a polyimide film (manufactured by Toray DuPont Co., Ltd., trade name; Kapton 50EN-S) is laminated on the opposite side of the side where the adhesive sheet is in contact with the printed board. ; 160°C, pressure; 3.5 MPa, time; Pressing was performed under the conditions for 60 minutes. This copper foil-attached test piece was subjected to 40°C, relative humidity; After standing at 80% for 72 hours, it was immersed in a solder bath set at each evaluation temperature for 10 seconds, and the adhesion state was observed to confirm the presence or absence of defects such as foaming, swelling, and peeling. Heat resistance was expressed as the upper limit temperature at which no defects occurred, for example, “260° C.” means that no defects were confirmed by evaluation in a 260° C. solder bath.

[Measurement of Peel Strength]

Width of double-sided copper clad laminate (Nitetsu Chemical & Materials Co., Ltd. product name; Espanex MB12-25-12UEG); 50 mm, length; After cutting to 100 mm, an adhesive sheet is placed on the copper foil side of the sample from which the copper foil on one side has been removed by etching, and a polyimide film (manufactured by Toray DuPont Co., Ltd., trade name; Kapton 50EN-S) is further laminated on the adhesive sheet. and temperature; 160°C, pressure; Pressing was performed under the conditions of 3.5 MPa and time: 60 minutes. The laminate was cut to a width of 5 mm of the test piece and pulled at a speed of 50 mm/min in the 90° direction of the test piece using a tensile tester (manufactured by Toyo Seiki Corporation, trade name; Strograph VE). The peel strength of the adhesive layer and the copper foil was measured.

[Method for evaluating flame retardancy]

A polyimide film (manufactured by Toray DuPont Co., Ltd., trade name; Kapton 50EN-S) was laminated on both sides of the adhesive sheet, and the temperature was adjusted; 160°C, pressure; 3.5 MPa, time; Pressing was performed under the conditions of 60 minutes. Cut the sample to 200 ± 5 mm × 50 ± 1 mm, roll it into a cylindrical shape with a diameter of about 12.7 mm and a length of 200 ± 5 mm, prepare a test piece conforming to the UL94VTM standard, and conduct a combustion test, VTM-0 A case that satisfies the judgment criteria of The case where the criterion of VTM-1 was satisfied was referred to as "A", and the case where the criterion of VTM-1 was not met was referred to as "Disabled".

(Synthesis Example 2-1)

In a 1000ml separable flask, 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 were put, and mixed well at 40° C. for 1 hour to prepare a polyamic acid solution. did This polyamic acid solution was heated to 190° C., heated and stirred for 10 hours, and imidized by adding 125 g of xylene to prepare polyimide solution 2-1 (solid content; 30% by weight, weight average molecular weight; 80,900). .

[Example 2-1]

To 100 g of the polyimide solution 2-1 prepared in Synthesis Example 2-1, 1.09 g of N-12 and 7.50 g of Filler 1 were blended, and xylene was added to dilute and stirred so that the solid content became 30% by weight, followed by stirring to obtain a polyimide Varnish 2-1a was prepared.

[Examples 2-2 to 2-8]

Polyimide varnishes 2-2a to 2-8a were prepared in the same manner as in Example 2-1 except that the blending amounts of the filler 1 and the filler 2 were changed as shown in Table 2-1.

[Comparative Example 2-1]

Polyimide varnish 2-9a was prepared in the same manner as in Example 2-1 except that filler 1 was not blended.

[Table 2-1]

[Example 2-9]

An adhesive sheet 2-1b (thickness: 25 µm) was prepared by applying the polyimide varnish 2-1a prepared in Example 2-1 to one side of a release-treated PET film, drying it at 80°C for 15 minutes, and peeling it off. .

Various evaluation results of the adhesive sheet 2-1b are as follows.

relative permittivity; 2.7, dielectric loss tangent; 0.0015, tensile modulus; 0.6 GPa, maximum elongation; 165%, Tg; 56°C, film retention; Good, solder heat resistance test (dry); 320℃, solder heat resistance test (moisture absorption); 260°C, Peel Strength; 1.8 kN/m, flame retardant; Good

[Example 2-10]

An adhesive sheet 2-2b was prepared in the same manner as in Example 2-9 using polyimide varnish 2-2a.

Various evaluation results of the adhesive sheet 2-2b are as follows.

relative permittivity; 2.9, dielectric loss tangent; 0.0013, tensile modulus; 0.5 GPa, maximum elongation; 77%, Tg; 56°C, film retention; Good, solder heat resistance test (dry); 320℃, solder heat resistance test (moisture absorption); 260°C, Peel Strength; 1.8 kN/m, flame retardant; Good

[Example 2-11]

An adhesive sheet 2-3b was prepared in the same manner as in Example 2-9 using polyimide varnish 2-3a.

Various evaluation results of the adhesive sheet 2-3b are as follows.

relative permittivity; 2.8, dielectric loss tangent; 0.0012, tensile modulus; 0.6 GPa, maximum elongation; 59%, Tg; 56°C, film retention; Good, solder heat resistance test (dry); 320℃, solder heat resistance test (moisture absorption); 270°C, Peel Strength; 1.8 kN/m, flame retardant; Good

[Example 2-12]

An adhesive sheet 2-4b was prepared in the same manner as in Example 2-9 using polyimide varnish 2-4a.

Various evaluation results of the adhesive sheet 2-4b are as follows.

relative permittivity; 2.8, dielectric loss tangent; 0.0011, tensile modulus; 0.8 GPa, maximum elongation; 31%, Tg; 56°C, film retention; Good, solder heat resistance test (dry); 320℃, solder heat resistance test (moisture absorption); 280°C, Peel Strength; 1.9 kN/m, flame retardant; Good

[Example 2-13]

An adhesive sheet 2-5b was prepared in the same manner as in Example 2-9 using polyimide varnish 2-5a.

Various evaluation results of the adhesive sheet 2-5b are as follows.

relative permittivity; 2.8, dielectric loss tangent; 0.0016, tensile modulus; 0.8 GPa, maximum elongation; 29%, Tg; 56°C, film retention; Good, solder heat resistance test (dry); 320℃, solder heat resistance test (moisture absorption); 270°C, Peel Strength; 1.9 kN/m, flame retardant; Good

[Example 2-14]

An adhesive sheet 2-6b was prepared in the same manner as in Example 2-9 using polyimide varnish 2-6a.

Various evaluation results of the adhesive sheet 2-6b are as follows.

relative permittivity; 2.7, dielectric loss tangent; 0.0015, tensile modulus; 0.6 GPa, maximum elongation; 169%, Tg; 56°C, film retention; Good, solder heat resistance test (dry); 320℃, solder heat resistance test (moisture absorption); 260°C, Peel Strength; 1.7 kN/m, flame retardant; Good

[Example 2-15]

An adhesive sheet 2-7b was prepared in the same manner as in Example 2-9 using polyimide varnish 2-7a.

Various evaluation results of the adhesive sheet 2-7b are as follows.

relative permittivity; 2.8, dielectric loss tangent; 0.0012, tensile modulus; 0.7 GPa, maximum elongation; 28%, Tg; 56°C, film retention; Good, solder heat resistance test (dry); 320℃, solder heat resistance test (moisture absorption); 280°C, Peel Strength; 1.8 kN/m, flame retardant; Good

[Example 2-16]

An adhesive sheet 2-8b was prepared in the same manner as in Example 2-9 using polyimide varnish 2-8a.

Various evaluation results of the adhesive sheet 2-8b are as follows.

relative permittivity; 2.6, dielectric loss tangent; 0.0016, tensile modulus; 0.5 GPa, maximum elongation; 177%, Tg; 56°C, film retention; Good, solder heat resistance test (dry); 320℃, solder heat resistance test (moisture absorption); 260°C, Peel Strength; 1.7 kN/m, flame retardant; go

[Comparative Example 2-2]

An adhesive sheet 2-9b was prepared in the same manner as in Example 2-9 using polyimide varnish 2-9a.

Various evaluation results of the adhesive sheet 2-9b are as follows.

relative permittivity; 2.6, dielectric loss tangent; 0.0017, tensile modulus; 0.4 GPa, maximum elongation; 197%, Tg; 56°C, film retention; Good, solder heat resistance test (dry); 320℃, solder heat resistance test (moisture absorption); 220°C, Peel Strength; 1.6 kN/m, flame retardant; impossible

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

[Table 2-2]

In Table 2-2, in comparison with the adhesive sheet 2-9b of Comparative Example 2-2, the adhesive sheets 2-1b to 2-8b of Examples 2-9 to 2-16 in which the filler 1 and the filler 2 were added were, It was confirmed that the dielectric properties and the solder heat resistance temperature (moisture absorption) were improved. From these results, in the adhesive sheet as a resin film according to the present embodiment, a reduction in transmission loss in a high frequency band of, for example, 20 GHz can be expected. Further, compared with the adhesive sheet 2-9b of Comparative Example 2-2, the adhesive sheets 2-1b to 2-8b of Examples 2-9 to 2-16 to which fillers 1 and 2 were added maintain flexibility and film retention properties. It was confirmed that the heat resistance, peel strength and flame retardancy of the moisture absorption solder were improved.

As shown in the above examples, the addition of cristobalite silica particles to the DDA/BTDA-based polyimide showed a clear effect of reducing the dielectric loss tangent.

In addition, when the flame retardancy was evaluated by the layer composition of the polyimide film/adhesive layer/polyimide film, it was confirmed that the adhesive layer containing cristobalite silica particles exhibited flame retardancy of VTM-1 level or higher.

In addition, the adhesive sheet obtained in each Example maintained the shape as a film in the blending amount of cristobalite silica particles within the practical range, and the adhesive force to polyimide or copper was also improved. Although the mechanism of the improvement of adhesive force has not been clearly elucidated, it is estimated that the improvement of the elastic modulus of the adhesive sheet may be contributing to this.

In addition, the solder heat resistance (dry/moisture absorption) of the adhesive sheet obtained in Example was equal to or higher than that of Comparative Example in which cristobalite silica particles were not incorporated, indicating desirable properties as an adhesive for high-frequency multilayer FPC.

From the above results, it was confirmed that the resin film according to the present embodiment is 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 are based on the following.

[Evaluation of genetic characteristics]

<Liquid crystalline polymer filler>

The dimethylacetamide dispersion of the liquid crystalline polymer filler adjusted to 30 weight% of solid content was apply|coated to the smooth surface of copper foil, and it dried at 120 degreeC for 10 minutes. Thereafter, the temperature was raised stepwise from 200°C to 360°C over 10 minutes, and the copper foil of the obtained laminate was etched and removed to obtain a film of liquid crystalline polymer.

Using a Vector Network Analyzer (manufactured by Keysight Technologies, trade name; Vector Network Analyzer E8363C) and a split post dielectric resonator (SPDR resonator), the obtained liquid crystalline polymer film was subjected to temperature; 23°C, humidity; After standing for 24 hours under the condition of 50%, the relative permittivity 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 an SPDR resonator, the resin film pressed under the conditions of a temperature of 160°C, a pressure of 3.5 MPa, and a time period of 60 minutes was subjected to temperature; 23°C, humidity; After allowing to stand for 24 hours under the condition of 50%, the relative permittivity and dielectric loss tangent at a frequency of 20 GHz were measured.

[Measurement of tensile modulus and maximum elongation]

Tensile modulus and maximum elongation were measured by the following procedure. First, using a tension tester (Tensilon manufactured by Orientec Co., Ltd.), a test piece (width 12.7 mm × length 127 mm) was prepared from a resin film. A tensile test was performed using this test piece at 50 mm/min, and the tensile modulus and maximum elongation at 25°C were obtained.

[Measurement of glass transition temperature (Tg)]

At the glass transition temperature (Tg), 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 was cut into a 5 mm × 20 mm size test piece, and a dynamic viscoelasticity measuring device (DMA: UB) (UBM) product, trade name; E4000F) was measured from 30°C to 300°C at a temperature increase rate of 4°C/min and a frequency of 11Hz, and the temperature at which the elastic modulus change (tanδ) was maximized was defined as the glass transition temperature.

[Evaluation of film retention properties]

Film retention was evaluated by the following procedure. The resin film was cut out into a test piece having a width of 20 mm and a length of 20 mm, folded so that fold lines were formed along a diagonal line, and then returned to the original state and the state of the film was observed. At this time, the thing which did not crack in the test piece even after folding and unfolding was set as "good", and the thing which cracked even in a part was set as "impossible".

[Solder heat resistance test (dry)]

Circuit processing is performed on a polyimide copper clad laminate (Nittetsu Chemical & Materials Co., Ltd. product name: Espanex MB12-25-12UEG), and a circuit of wiring width/wiring spacing (L/S) = 1mm/1mm is obtained. The formed printed board was prepared. A resin film is placed on the wiring of the printed board, and a polyimide film (Toray DuPont Co., Ltd. product name: Kapton 50EN-S) is laminated on the opposite side of the side where the resin film is in contact with the printed board. ; 160°C, pressure; 3.5 MPa, time; Pressing was performed under the conditions for 60 minutes. After the copper foil-attached test piece was dried at 105° C., it was immersed in a solder bath set at each evaluation temperature for 10 seconds, and the adhesion state was observed to confirm the presence or absence of defects such as foaming, swelling, and peeling. Heat resistance was expressed as the upper limit temperature at which no defects occurred. For example, “320° C.” means that no defects were confirmed by evaluation in a 320° C. solder bath.

[Solder heat resistance test (moisture absorption)]

Circuit processing is performed on polyimide copper clad laminate (Nittetsu Chemical & Materials Co., Ltd. product, trade name: Espanex MB12-25-12UEG), and wiring width / wiring spacing (L/S) = 1mm/1mm circuit A printed board on which was formed was prepared. Place the resin film on the wiring of the printed board, and after laminating the polyimide film (Toray DuPont Co., Ltd. product name: Kapton 50EN-S) on the opposite side of the side where the resin film is in contact with the printed board, the temperature; 160°C, pressure; 3.5 MPa, time; Pressing was performed under the conditions for 60 minutes. This copper foil-attached test piece was left to stand at 40°C and 80% relative humidity for 72 hours, then immersed in a solder bath set at each evaluation temperature for 10 seconds, and the adhesion state was observed, and defects such as foaming, swelling, and peeling were observed. The presence or absence of was confirmed. Heat resistance was expressed as the upper limit temperature at which no defects occurred, for example, “260° C.” means that no defects were confirmed by evaluation in a 260° C. solder bath.

[Measurement of Peel Strength]

Peel strength was measured by the following method. The copper foil on one side of the double-sided polyimide copper clad laminate (manufactured by Nittetsu Chemical & Materials Co., Ltd., trade name: Espanex MB12-25-12UEG) is cut to a width of 50 mm and a length of 100 mm, and the copper foil of the other side is etched. Place a resin film, and laminate a polyimide film (manufactured by Toray DuPont Co., Ltd., trade name: Kapton 50EN-S) on the opposite side to the copper clad laminate of the resin film, temperature; 160°C, pressure; 3.5 MPa, time; Pressing was performed under the conditions of 60 minutes. The adhesive layer when the laminate was cut to a width of 5 mm of the test piece and pulled at a speed of 50 mm/min in the 90° direction of the test piece using a tensile tester (manufactured by Toyo Seiki Seisakusho Co., Ltd., Strograph VE) The peel strength of the resin film and copper foil as

[Method for evaluating flame retardancy]

The flame retardancy was evaluated by the following method. A polyimide film (manufactured by Toray DuPont Co., Ltd., trade name: Kapton 50EN-S) was laminated on both sides of a resin film laminated with 4 sheets so as to have a thickness of 100 µm, temperature; 160°C, pressure; 3.5 MPa, time; Pressing was performed under the conditions of 60 minutes. Cut the sample to 200±5mm × 50±1mm, roll it into a tubular shape with a diameter of about 12.7mm and a length of 200±5mm. If it was 0-5 seconds, it was “◎” (good), if it was 6-10 seconds, it was “○” (good), if it was 11-20 seconds, it was “△” (A), and when it exceeded 21 seconds, it was “×” (impossible). .

[Synthesis Example 3-1]

In a 1000ml separable flask, 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 were put, and mixed well at 40° C. for 1 hour to prepare a polyamic acid solution. did The polyamic acid solution was heated to 190° C., heated and stirred for 10 hours, and imidized by adding 125 g of xylene to prepare a polyimide solution 3-1 (solid content: 30 wt%, weight average molecular weight: 80,900). .

[Example 3-1]

To 100 g of the polyimide solution 3-1 prepared in Synthesis Example 3-1, 1.09 g of N-12 and 7.50 g of LCP filler were blended, and xylene was added to dilute and stirred so that the solid content became 30 wt%, and the polyimide Varnish 3-1a was prepared.

[Examples 3-2-3-4]

Polyimide varnishes 3-2a to 3-4a were prepared in the same manner as in Example 3-1 except that the blending amount of the LCP filler was changed as shown in Table 3-1.

[Example 3-5]

To 100 g of 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 xylene was added to dilute so that the solid content was 30 wt%. And by stirring, polyimide varnish 3-5a was prepared.

[Examples 3-6 to 3-7]

Polyimide varnishes 3-6a to 3-7a were prepared in the same manner as in Example 3-5, except that the blending amount of the LCP filler was changed as shown in Table 3-1.

[Examples 3-8 to 3-10]

Polyimide varnishes 3-8a to 3- in the same manner as in Example 3-5, except that the flame retardant 2 was used in the amount shown in Table 3-1 instead of the flame retardant 1 and the LCP filler was blended as shown in Table 3-1. 10a was prepared.

[Comparative Example 3-1]

Polyimide varnish 3-11a was prepared in the same manner as in Example 3-1, except that the LCP filler was not blended.

[Comparative Example 3-2]

Polyimide varnish 3-12a was prepared in the same manner as in Example 3-5 except that the LCP filler was not blended.

[Table 3-1]

[Example 3-11]

The polyimide varnish 3-1a prepared in Example 3-1 was applied to one side of the release-treated PET film, dried at 80° C. for 15 minutes, and peeled to prepare a resin film 3-1b (thickness: 25 μm). .

Various evaluation results of the resin film 3-1b are as follows.

relative permittivity; 2.7, dielectric loss tangent; 0.0015, tensile modulus; 0.6 GPa, maximum elongation; 131%, Tg; 54°C, film retention; Good, solder heat resistance test (dry); 320℃, solder heat resistance test (moisture absorption); 260°C, Peel Strength; 1.6 kN/m, flame retardant; ○

[Example 3-12]

Polyimide varnish 3-2a was used and a resin film 3-2b was prepared in the same manner as in Example 3-11.

Various evaluation results of the resin film 3-2b are as follows.

relative permittivity; 2.7, dielectric loss tangent; 0.0014, tensile modulus; 0.7 GPa, maximum elongation; 80%, Tg; 54°C, film retention; Good, solder heat resistance test (dry); 320℃, solder heat resistance test (moisture absorption); 260°C, Peel Strength; 1.5 kN/m, flame retardant; ○

[Example 3-13]

Polyimide varnish 3-3a was used and a resin film 3-3b was prepared in the same manner as in Example 3-11.

Various evaluation results of the resin film 3-3b are as follows.

relative permittivity; 2.8, dielectric loss tangent; 0.0014, tensile modulus; 0.7 GPa, maximum elongation; 38%, Tg; 58°C, film retention; Good, solder heat resistance test (dry); 320℃, solder heat resistance test (moisture absorption); 270°C, Peel Strength; 1.2 kN/m, flame retardant; ○

[Example 3-14]

A resin film 3-4b was prepared in the same manner as in Example 3-11 using polyimide varnish 3-4a.

Various evaluation results of the resin film 3-4b are as follows.

relative permittivity; 2.9, dielectric loss tangent; 0.0013, tensile modulus; 0.8 GPa, maximum elongation; 18%, Tg; 58°C, film retention; Good, solder heat resistance test (dry); 320℃, solder heat resistance test (moisture absorption); 280°C, Peel Strength; 1.2 kN/m, flame retardant; ○

[Example 3-15]

A resin film 3-5b was prepared in the same manner as in Example 3-11, using polyimide varnish 3-5a.

Various evaluation results of the resin film 3-5b are as follows.

relative permittivity; 2.7, dielectric loss tangent; 0.0016, tensile modulus; 0.5 GPa, maximum elongation; 100%, Tg; 54°C, film retention; Good, solder heat resistance test (dry); 320℃, solder heat resistance test (moisture absorption); 270°C, Peel Strength; 2.0 kN/m, flame retardant; ◎

[Example 3-16]

Polyimide varnish 3-6a was used, and resin film 3-6b was prepared in the same manner as in Example 3-11.

Various evaluation results of the resin film 3-6b are as follows.

relative permittivity; 2.8, dielectric loss tangent; 0.0015, tensile modulus; 0.7 GPa, maximum elongation; 33%, Tg; 58°C, film retention; Good, solder heat resistance test (dry); 320℃, solder heat resistance test (moisture absorption); 270°C, Peel Strength; 1.3 kN/m, flame retardant; ◎

[Example 3-17]

Polyimide varnish 3-7a was used, and in the same manner as in Example 3-11, a resin film 3-7b was prepared.

Various evaluation results of the resin film 3-7b are as follows.

relative permittivity; 2.8, dielectric loss tangent; 0.0014, tensile modulus; 0.7 GPa, maximum elongation; 11%, Tg; 58°C, film retention; Good, solder heat resistance test (dry); 320℃, solder heat resistance test (moisture absorption); 280°C, Peel Strength; 0.9 kN/m, flame retardant; ◎

[Example 3-18]

Using polyimide varnish 3-8a, in the same manner as in Example 3-11, a resin film 3-8b was prepared.

Various evaluation results of the resin film 3-8b are as follows.

relative permittivity; 2.7, dielectric loss tangent; 0.0015, tensile modulus; 0.5 GPa, maximum elongation; 114%, Tg; 54°C, film retention; Good, solder heat resistance test (dry); 320℃, solder heat resistance test (moisture absorption); 280°C, Peel Strength; 1.4 kN/m, flame retardant; ◎

[Example 3-19]

Polyimide varnish 3-9a was used, and a resin film 3-9b was prepared in the same manner as in Example 3-11.

Various evaluation results of the resin film 3-9b are as follows.

relative permittivity; 2.8, dielectric loss tangent; 0.0014, tensile modulus; 0.6 GPa, maximum elongation; 52%, Tg; 56°C, film retention; Good, solder heat resistance test (dry); 320℃, solder heat resistance test (moisture absorption); 280°C, Peel Strength; 1.0 kN/m, flame retardant; ◎

[Example 3-20]

Polyimide varnish 3-10a was used, and resin film 3-10b was prepared in the same manner as in Example 3-11.

Various evaluation results of the resin film 3-10b are as follows.

relative permittivity; 2.9, dielectric loss tangent; 0.0013, tensile modulus; 0.6 GPa, maximum elongation; 22%, Tg; 56°C, film retention; Good, solder heat resistance test (dry); 320℃, solder heat resistance test (moisture absorption); 290°C, Peel Strength; 0.7 kN/m, flame retardant; ◎

[Comparative Example 3-3]

Polyimide varnish 3-11a was used and a resin film 3-11b was prepared in the same manner as in Example 3-11.

Various evaluation results of the resin film 3-11b are as follows.

relative permittivity; 2.6, dielectric loss tangent; 0.0017, tensile modulus; 0.4 GPa, maximum elongation; 197%, Tg; 56°C, film retention; Good, solder heat resistance test (dry); 320℃, solder heat resistance test (moisture absorption); 220°C, Peel Strength; 1.6 kN/m, flame retardant; ×

[Comparative Example 3-4]

Polyimide varnish 3-12a was used and a resin film 3-12b was prepared in the same manner as in Example 3-11.

Various evaluation results of the resin film 3-12b are as follows.

relative permittivity; 2.6, dielectric loss tangent; 0.0018, tensile modulus; 0.8 GPa, maximum elongation; 226%, Tg; 56°C, film retention; Good, solder heat resistance test (dry); 320℃, solder heat resistance test (moisture absorption); 280°C, Peel Strength; 1.7 kN/m, flame retardant; △

Table 3-2 summarizes the above results.

[Table 3-2]

From Table 3-2, compared with the resin film 3-11b of Comparative Example 3-3, the resin films 3-1b to 3-4b of Examples 3-11 to 3-14 with LCP filler added had dielectric loss tangent and flame retardancy. And it was confirmed that the solder heat resistance temperature (moisture absorption) was improved. The dielectric loss tangent of the resin film decreases as the amount of LCP filler, which has a lower dielectric loss tangent than that of DDA-based thermoplastic polyimide, increases. In addition, by blending a DDA-based thermoplastic polyimide that is easily combusted with an LCP filler having a high aromatic ring concentration, an excellent flame retardant effect is exhibited. Further, it is considered that the heat resistance of the solder is improved because the moisture absorption content is decreased and the elastic modulus is improved by the addition of the LCP filler.

In addition, the resin films 3-1b to 3-4b maintain film properties and also have an adhesive strength exceeding 0.6 kN/m normally required for production of a flexible printed wiring board. It is suitable for creation of the flexible printed wiring board using the high frequency band of 10 GHz or more. Since the DDA-based thermoplastic polyimide has a large elongation, film properties can be maintained even if an LCP filler is added. Moreover, since Tg is sufficiently low with respect to a press temperature, while resin tracks the fine unevenness|corrugation of the copper foil surface, it is thought that adhesiveness is ensured by the carbonyl group of BTDA used as an acid anhydride.

Further, from Table 3-2, compared with the resin film 3-12b of Comparative Example 3-4, the resin films 3-5b to 3-10b of Examples 3-15 to 3-20 to which LCP filler was added had a dielectric loss tangent. While it falls, the flame retardance is greatly improved, and it is suitable as a material of the flexible printed wiring board corresponding to the high frequency in which thickness-ization of a dielectric material layer is progressing, for example.

In the case of a combination of only the DDA-based thermoplastic polyimide and the phosphorus-based flame retardant, the char-forming effect of the phosphorus-based flame retardant is not sufficiently expressed in many cases because the aromatic ring concentration in the DDA-based thermoplastic polyimide is low, Example 3-15 As shown in 3-20, it is thought that the flame retardant effect by the phosphorus flame retardant is increased due to the result that the aromatic ring concentration in the composition is increased by using the combination of the DDA-based thermoplastic polyimide, the LCP filler, and the phosphorus-based flame retardant.

As mentioned above, although embodiment of this invention was described in detail for the purpose of illustration, this invention is not limited by the said embodiment, and various modifications are possible.

This application is a Japanese Patent Application No. 2019-196671 filed in Japan on October 29, 2019, Japanese Patent Application No. 2019-238107 filed in Japan on December 27, 2019 and a Japanese Patent Application As claiming priority under No. 2019-238108, the entire contents of the application are incorporated herein by reference.

Claims (22)

following (A) component and (B) component;
(A) A structure derived from a diamine component containing 40 mol% or more of a dimerdiamine composition containing as a main component dimerdiamine in which two terminal carboxylic acid groups of dimer acid are substituted with primary aminomethyl groups or amino groups with respect to the total diamine component a thermoplastic resin containing units, and
(B) at least one selected from aromatic condensed phosphate esters, silica particles, or liquid crystalline polymer fillers
A resin composition containing
According to claim 1,
The component (A) is a polyimide obtained by reacting a tetracarboxylic anhydride component with a diamine component containing 40 mol% or more of the dimer diamine composition with respect to all the diamine components, and the component (B) is the aromatic condensed phosphoric acid. ester,
The resin composition in which the weight ratio of the said (B) component with respect to the said (A) component exists in the range of 0.05-0.7.
3. The method of claim 2,
The resin composition in which the weight ratio of the said (B) component with respect to the said (A) component exists in the range of 0.2-0.5.
3. The method of claim 2,
The resin composition whose weight ratio of the phosphorus derived from (B) component with respect to the said (A) component exists in the range of 0.01-0.1.
3. The method of claim 2,
The resin composition in which the weight ratio of the phosphorus derived from (B) component with respect to the dimerdiamine composition in the said (A) component exists in the range of 0.01-0.15.
3. The method of claim 2,
A resin composition further comprising an amino compound having at least two primary amino groups as functional groups.
According to claim 1,
The component (A) is a polyamic acid or polyimide formed by reacting a tetracarboxylic anhydride component with a diamine component containing 40 mol% or more of the dimer diamine composition with respect to all the diamine components, and the component (B) is It is a silica particle having a cristobalite crystal phase or a quartz crystal phase,
The resin composition in which the said (B) component exists in the range of 5 to 60 weight% with respect to the sum total of the said (A) component (however, polyamic acid is converted into the imidated polyimide) and the said (B) component.
8. The method of claim 7,
The component (B) is a peak derived from a cristobalite crystal phase and a quartz crystal phase with respect to the total area of all peaks derived from SiO ₂ in the range of 2θ = 10° to 90° of the X-ray diffraction spectrum by CuKα ray. A resin composition having a total area ratio of 20% by weight or more.
8. The method of claim 7,
The resin composition having an average particle diameter D ₅₀ of which the cumulative value in a frequency distribution curve obtained by volume-based particle size distribution measurement by a laser diffraction scattering method of the component (B) is 50% in the range of 6 to 20 µm.
According to claim 1,
The component (A) is a polyimide obtained by reacting a tetracarboxylic acid anhydride component with a diamine component containing 40 mol% or more of the dimerdiamine composition with respect to all the diamine components, and the component (B) is the liquid crystal polymer is a filler,
The resin composition in which the said (B)component exists in the range of 15-50 volume% with respect to the sum total of the said (A)component and the said (B)component.
11. The method of claim 10,
When the dielectric loss tangent in 10 GHz of the said (A) component is Dfa, and the dielectric loss tangent in 10 GHz of the said (B) component is Dfb, Dfb is less than 0.0019, Dfa>Dfb The resin composition.
11. The method of claim 10,
A resin composition in which 15 to 30% by weight of a phosphorus-based flame retardant is further added with respect to 100% by weight of the nonvolatile organic compound component of the resin composition.
11. The method of any one of claims 2, 7, and 10,
The component (A) contains 90 mole parts or more in total of the tetracarboxylic acid anhydride represented by the following general formulas (1) and/or (2) with respect to 100 mole parts of the tetracarboxylic acid anhydride component.
(Formula 1)

[In the general formula (1), X represents a single bond or a divalent group selected from the following formula, and in the general formula (2), the cyclic moiety represented by Y is a 4-membered ring, a 5-membered ring, a 6-membered ring, a 7-membered ring, or an 8-membered ring indicates that a selected cyclic saturated hydrocarbon group is formed]
(Formula 2)

[In the above formula, Z represents —C ₆ H ₄ —, —(CH ₂ )n— or —CH ₂ —CH(—O—C(=O)—CH ₃ )—CH ₂ —, and n is represents an integer from 1 to 20]
A resin film comprising a thermoplastic resin layer, the following (A) component and (B) component;
(A) A structure derived from a diamine component containing 40 mol% or more of a dimerdiamine composition containing as a main component dimerdiamine in which two terminal carboxylic acid groups of dimer acid are substituted with primary aminomethyl groups or amino groups with respect to the total diamine component a thermoplastic resin containing units, and
(B) at least one selected from aromatic condensed phosphate esters, silica particles, or liquid crystalline polymer fillers
A resin film comprising a.
15. The method of claim 14,
A resin film having a thickness in the range of 15 to 100 μm.
15. The method of claim 14,
A resin film in which the component (B) consists of silica particles having a cristobalite crystal phase or a quartz crystal phase, and the content is within the range of 3 to 41 vol% based on the total of the component (A) and the component (B).
15. The method of claim 14,
The resin film in which the said (B) component consists of the said liquid crystalline polymer filler, and the content exists in the range of 15-40 volume% with respect to the sum total of the said (A) component and the said (B) component.
A laminate comprising a substrate and an adhesive layer laminated on at least one surface of the substrate,
The said adhesive layer is laminated body, characterized in that it consists of the resin film of Claim 14.
A coverlay film comprising: a film material layer for a coverlay; and an adhesive layer laminated on the film material layer for a coverlay;
The adhesive layer is a coverlay film, characterized in that consisting of the resin film of claim 14.
A resin-containing copper foil in which an adhesive layer and a copper foil are laminated,
The resin-containing copper foil, characterized in that the adhesive layer is made of the resin film of claim 14.
A metal foil laminate comprising an insulating resin layer and a metal layer laminated on at least one surface of the insulating resin layer,
At least one layer of the insulating resin layer is a metal clad laminate, characterized in that it consists of the resin film of claim 14.
A circuit board formed by wiring the metal layer of the metal clad laminate of claim 21 .