TWI743345B - Polyimide, adhesive, film-like adhesive material, adhesive layer, adhesive sheet, copper foil with resin, copper clad laminate, printed circuit board, and multilayer circuit board and manufacturing method thereof - Google Patents

Abstract

The problem to be solved by the present invention is to provide a polyimide, an adhesive, a film-like adhesive material, an adhesive layer, an adhesive sheet, a resin-attached copper foil, a copper-clad laminate, and a printed circuit board and a manufacturing method thereof. The solution of the present invention is to provide: a polyimide, which is a reactant of a monomer group containing aromatic tetracarboxylic anhydride and diamine, and contains a stretchy group in the polymer backbone, and the diamine contains Dimer diamine; an adhesive containing polyimide, crosslinking agent and organic solvent; and, a film-like adhesive material, adhesive layer, adhesive sheet, copper foil with resin, copper clad laminate, printing Circuit board, multilayer circuit board and manufacturing method thereof.

Description

Polyimide, adhesive, film-like adhesive material, adhesive layer, adhesive sheet, copper foil with resin, copper-clad laminate, printed circuit board, and multilayer circuit board and manufacturing method thereof

This disclosure relates to a polyimide, an adhesive, a film-like adhesive material, an adhesive layer, an adhesive sheet, a copper foil with resin, a copper-clad laminate, a printed circuit board, and a multilayer circuit board and a manufacturing method thereof.

Various well-known adhesives have been used in the manufacture of mobile communication devices such as mobile phones and smart phones, or base station devices, network-related electronic devices such as servers/routers, and printed circuit boards included in mainframe computers.

The applicant proposed "a polyimide-based adhesive composition, which comprises a polyimide resin, a thermosetting resin, a flame retardant, and an organic solvent. The polyimide resin is made of aromatic tetracarboxylic acids and containing It is formed by the reaction of the diamines of the specific dimer diamine of 30 mol% or more" (refer to Patent Document 1). [Prior Art Document] (Patent Document)

Patent Document 1: Japanese Patent No. 5534378

[Problem to be solved by the invention] In recent years, in the above-mentioned network-related electronic equipment, it is necessary to transmit and process large-capacity information at a low loss and at a high speed. As a result, the electrical signals processed by the printed circuit boards of these products are also increasing. Frequency development. High-frequency electrical signals are prone to attenuation, so it is necessary to further reduce the transmission loss in the printed circuit board. Therefore, the adhesives generally used in printed wiring boards require low dielectric constant and low dielectric loss tangent (also called low dielectric properties).

However, Patent Document 1 has not studied low dielectric loss tangent. In addition, in recent years, there has been a problem that adhesives with low dielectric loss tangent are particularly required with the increase in high frequency of electrical signals. [Technical means to solve the problem]

As a result of intensive research, the inventors found that the above-mentioned problems can be solved by using a prescribed polyimide.

。 (項目2) 如上述項目所述的聚醯亞胺，其中，前述二胺包含下述含茀骨架之二胺，

上述式中，R¹ 和R² 中的任一個表示具有胺基之基團，另一個表示氫原子、羥基、烷基或鹵素原子，R³ 和R4中的任一個表示具有胺基之基團，另一個表示氫原子、羥基、烷基或鹵素原子。 (項目3) 如上述項目中任一項所述的聚醯亞胺，其中，前述二胺包含二胺基聚矽氧烷。 (項目4) 如上述項目中任一項所述的聚醯亞胺，其中，前述芳香族四羧酸酐與前述二胺的莫耳比[芳香族四羧酸酐/二胺]為1.0～1.5。 (項目5) 一種黏著劑，其包含上述項目中任一項所述的聚醯亞胺、交聯劑及有機溶劑。 (項目6) 如上述項目所述的黏著劑，其中，前述交聯劑為選自由環氧化物、苯并噁嗪、雙馬來醯亞胺及氰酸酯所組成之群組中的至少一種。 (項目7) 如上述項目所述的黏著劑，其中，前述環氧化物為下述結構的環氧化物，

上述式中，Y表示伸苯基或伸環己基。 (項目8) 如上述項目中任一項所述的黏著劑，其中，相對於以固體成分換算為100質量份的前述聚醯亞胺，包含5～900質量份的前述交聯劑，且包含150～900質量份的前述有機溶劑。 (項目9) 一種薄膜狀黏著材料，其包含上述項目中任一項所述的黏著劑的加熱硬化物。 (項目10) 一種黏著層，其包含上述項目中任一項所述的黏著劑、或上述項目的薄膜狀黏著材料。 (項目11) 一種黏著片，其包含上述項目所述的黏著層、及支撐薄膜。 (項目12) 一種附有樹脂之銅箔，其包含上述項目所述的黏著層、及銅箔。 (項目13) 一種覆銅積層板，其包含上述項目所述的附有樹脂之銅箔、及銅箔。 (項目14) 一種覆銅積層板，其包含上述項目所述的附有樹脂之銅箔、及絕緣性片。 (項目15) 一種印刷線路板，其在上述項目中任一項所述的覆銅積層板的銅箔面上具有電路圖案。 (項目16) 一種多層線路板，其包含： 印刷線路板(1)或印刷電路板(1)、上述項目所述的黏著層、及印刷線路板(2)或印刷電路板(2)。 (項目17) 一種多層線路板的製造方法，其包括下述步驟1和步驟2： 步驟1，是藉由使上述項目中任一項所述的黏著劑、或上述項目所述的薄膜狀黏著材料，與印刷線路板(1)或印刷電路板(1)的至少單面接觸，來製造附有黏著層之基材的步驟； 步驟2，是在該附有黏著層之基材上積層印刷線路板(2)或印刷電路板(2)，並在加熱和加壓下進行壓接的步驟。This disclosure provides the following items. (Item 1) A polyimide, which is a reactant of a monomer group containing an aromatic tetracarboxylic anhydride and a diamine, and contains the following extension group in the polymer main chain, and the diamine contains a dimer Diamine,

. (Item 2) The polyimide according to the above item, wherein the aforementioned diamine includes the following diamine containing a stilbene skeleton,

In the above formula, ^{any one of R 1} and R ² represents a group having an amine group, the other represents a hydrogen atom, a hydroxyl group, an alkyl group or a halogen atom, ^{and any one of R 3} and R4 represents a group having an amine group , The other represents a hydrogen atom, a hydroxyl group, an alkyl group or a halogen atom. (Item 3) The polyimide according to any one of the above items, wherein the diamine includes a diaminopolysiloxane. (Item 4) The polyimide according to any one of the above items, wherein the molar ratio of the aromatic tetracarboxylic anhydride to the diamine [aromatic tetracarboxylic anhydride/diamine] is 1.0 to 1.5. (Item 5) An adhesive comprising the polyimide described in any one of the above items, a crosslinking agent, and an organic solvent. (Item 6) The adhesive according to the above item, wherein the crosslinking agent is at least one selected from the group consisting of epoxides, benzoxazines, bismaleimides, and cyanate esters . (Item 7) The adhesive according to the above item, wherein the epoxide is an epoxide having the following structure,

In the above formula, Y represents phenylene or cyclohexylene. (Item 8) The adhesive according to any one of the above items, which contains 5 to 900 parts by mass of the crosslinking agent with respect to 100 parts by mass of the polyimide in terms of solid content, and contains 150 to 900 parts by mass of the aforementioned organic solvent. (Item 9) A film-like adhesive material comprising a heat-cured product of the adhesive according to any one of the above items. (Item 10) An adhesive layer comprising the adhesive according to any one of the above items, or the film-like adhesive material of the above items. (Item 11) An adhesive sheet comprising the adhesive layer described in the above item and a supporting film. (Item 12) A resin-attached copper foil comprising the adhesive layer described in the above item and copper foil. (Item 13) A copper clad laminate comprising the resin-attached copper foil and copper foil described in the above item. (Item 14) A copper-clad laminate comprising the resin-coated copper foil described in the above item and an insulating sheet. (Item 15) A printed wiring board having a circuit pattern on the copper foil surface of the copper clad laminate according to any one of the above items. (Item 16) A multilayer circuit board comprising: a printed circuit board (1) or a printed circuit board (1), the adhesive layer described in the above item, and a printed circuit board (2) or a printed circuit board (2). (Item 17) A method for manufacturing a multilayer circuit board, which includes the following steps 1 and 2: Step 1, by making the adhesive described in any of the above items or the film-like adhesion described in the above items The material is in contact with at least one side of the printed circuit board (1) or printed circuit board (1) to produce a substrate with an adhesive layer; step 2, is to laminate and print on the substrate with an adhesive layer Circuit board (2) or printed circuit board (2), and the step of crimping under heating and pressure.

In the present disclosure, one or more of the above-mentioned features can be provided in further combination in addition to the explicitly stated combination. [Effect of Invention]

By using the polyimide of the present invention, an adhesive with low dielectric loss tangent can be provided. The above-mentioned adhesive can be suitably used for high-frequency electronic parts such as high-function mobile terminals such as printed wiring boards.

In the entire specification of the present disclosure, the range of values such as each physical property value and content can be set appropriately (for example, selecting from the upper and lower limit values described in the following items). Specifically, regarding the numerical value α, when the upper limit of the numerical value α can be exemplified by A1, A2, A3, and the lower limit of the numerical value α can be exemplified by B1, B2, B3, etc., the range of the numerical value α can be exemplified by A1 or less, A2 Below, below A3, above B1, above B2, above B3, A1～B1, A1～B2, A1～B3, A2～B1, A2～B2, A2～B3, A3～B1, A3～B2, A3～B3, etc. .

。[Polyimine] The present disclosure provides a polyimide, which is a reactant of a monomer group including aromatic tetracarboxylic anhydride and diamine, and includes the following extension group in the polymer main chain, which Diamines include dimer diamines,

.

In the present disclosure, "including the extension group in the polymer main chain" means that the extension group is included in the longest chain constituting the polymer.

<Aromatic tetracarboxylic anhydride> Aromatic tetracarboxylic anhydride can be used individually or in 2 or more types. The aromatic tetracarboxylic acid anhydride can be exemplified by a tetracarboxylic acid anhydride containing a sulfonium skeleton, a symmetrical aromatic tetracarboxylic acid anhydride, and the like.

上述式中，R¹ 和R² 中的任一個表示具有酸酐基之基團，另一個表示氫原子、羥基、烷基或鹵素原子，R³ 和R4中的任一個表示具有酸酐基之基團，另一個表示氫原子、羥基、烷基或鹵素原子；或者，表示R¹ 和R² 及/或R³ 和R⁴ 一起形成酸酐基的基團。(Tetracarboxylic anhydride containing a sulphur skeleton) In one of the embodiments, the tetracarboxylic anhydride containing a sulphur skeleton is represented by the following general formula:

In the above formula, ^{any one of R 1} and R ² represents a group having an acid anhydride group, the other represents a hydrogen atom, a hydroxyl group, an alkyl group or a halogen atom, ^{and any one of R 3} and R4 represents a group having an acid anhydride group , The other represents a hydrogen atom, a hydroxyl group, an alkyl group or a halogen atom; or, represents a group in which R ¹ and R ² and/or R ³ and R ⁴ together form an acid anhydride group.

Examples of groups having an acid anhydride group include 3,4-dicarboxyphenoxy, 3,4-dicarboxyphenyl, and the like.

When R ¹ and R ² and/or R ³ and R ⁴ form an acid anhydride group together, the acid anhydride group formed can be exemplified by 3,4-dicarboxyphenyl.

Examples of alkyl groups include linear alkyl groups, branched alkyl groups, cycloalkyl groups, and the like.

The carbon number of the alkyl group is not particularly limited, and the upper limit can be exemplified: 30, 29, 25, 20, 15, 12, 10, 9, 8, 7, 6, 5, 4, 3, 2, etc.; the lower limit can be exemplified: 29, 25, 20, 15, 12, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, etc. In one embodiment, the carbon number of the alkyl group is preferably about 1-30, more preferably about 1-20, still more preferably about 1-16, particularly preferably about 1-12.

Examples of linear alkyl groups include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, and the like.

Examples of branched alkyl groups include isopropyl, isobutyl, isopentyl, isohexyl, and isodecyl.

Cycloalkyl can be exemplified by cyclopentyl, cyclohexyl, cycloheptyl and the like. In addition, one or more hydrogen atoms on each ring of the cycloalkyl group may be substituted with a linear alkyl group (the aforementioned exemplified group, etc.) or a branched alkyl group (the aforementioned exemplified group, etc.).

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Examples of tetracarboxylic acid anhydrides containing a stilbene skeleton include: 9,9'-bis[4-(3,4-dicarboxyphenoxy)phenyl] dianhydride, 9,9'-bis(3,4- Dicarboxyphenoxy) dianhydride and the like.

The upper limit of the content of the tetracarboxylic anhydride containing the sulphur skeleton in 100 mol% of aromatic tetracarboxylic anhydride can be exemplified: 100 mol%, 90 mol%, 80 mol%, 70 mol%, 60 mol% , 55 mol%, 50 mol%, 40 mol%, 30 mol%, 20 mol%, 10 mol%, etc.; the lower limit can be exemplified: 95 mol%, 90 mol%, 80 mol% , 70 mol%, 60 mol%, 50 mol%, 40 mol%, 30 mol%, 20 mol%, 10 mol%, 0 mol%, etc. In one embodiment, the content of the tetracarboxylic anhydride containing the sulphur skeleton in 100 mol% of the aromatic tetracarboxylic anhydride is preferably about 0-100 mol%, more preferably about 50-100 mol%.

The upper limit of the content of the tetracarboxylic anhydride containing the sulfur skeleton in 100% by mass of the aromatic tetracarboxylic anhydride can be exemplified: 100% by mass, 90% by mass, 80% by mass, 70% by mass, 60% by mass, 55% by mass, 50 Mass%, 40% by mass, 30% by mass, 20% by mass, 10% by mass, etc.; lower limit can be exemplified: 95% by mass, 90% by mass, 80% by mass, 70% by mass, 60% by mass, 50% by mass, 40% by mass %, 30% by mass, 20% by mass, 10% by mass, 0% by mass, etc. In one embodiment, the content of the tetracarboxylic anhydride containing the stilbene skeleton in 100% by mass of the aromatic tetracarboxylic anhydride is preferably about 0 to 100% by mass, more preferably about 50 to about 100% by mass.

The upper limit of the content of the tetracarboxylic acid anhydride containing the sulphur skeleton in 100 mol% of the monomer group can be exemplified: 75 mol%, 70 mol%, 60 mol%, 50 mol%, 40 mol%, 30 mol%, 20 mol%, 10 mol%, 5 mol%, etc.; the lower limit can be exemplified: 70 mol%, 60 mol%, 50 mol%, 40 mol%, 30 mol%, 20 mol%, 10 mol%, 5 mol%, 0 mol%, etc. In one embodiment, the content of the tetracarboxylic acid anhydride containing the stilbene skeleton in 100 mol% of the monomer group is preferably about 0 to 75 mol%.

The upper limit of the content of the tetracarboxylic acid anhydride containing the 茀 skeleton in 100% by mass of the monomer group can be exemplified: 75% by mass, 70% by mass, 60% by mass, 50% by mass, 40% by mass, 30% by mass, and 20% by mass %, 10 mass%, 5 mass%, etc.; the lower limit can be exemplified: 70 mass%, 60 mass%, 50 mass%, 40 mass%, 30 mass%, 20 mass%, 10 mass%, 5 mass%, 0 mass% Wait. In one embodiment, the content of the tetracarboxylic anhydride containing the stilbene skeleton in 100% by mass of the monomer group is preferably about 0 to about 75% by mass.

上述式中，X表示單鍵、-SO₂ -、-CO-、-O-、-O-C₆ H₄ -C(CH₃ )₂ -C₆ H₄ -O-、-COO-(CH₂ )_p -OCO-或-COO-H₂ C-HC(-O-C(=O)-CH₃ )-CH₂ -OCO-，p表示1～20的整數。(Symmetric aromatic tetracarboxylic anhydride) In this disclosure, "symmetric aromatic tetracarboxylic anhydride" means an aromatic tetracarboxylic anhydride having a symmetry axis (for example, C2 symmetry axis) in the molecule. The symmetrical aromatic tetracarboxylic acid anhydride can be exemplified by the symmetrical aromatic tetracarboxylic acid anhydride represented by the following general formula, etc.,

In the above formula, X represents a single bond, -SO ₂ -, _{-CO-, -O-, -OC 6} H ₄ -C(CH ₃ ) ₂ -C ₆ H ₄ -O-, -COO-(CH ₂ ) _p -OCO- or -COO-H ₂ C-HC(-OC(=O)-CH ₃ )-CH ₂ -OCO-, and p represents an integer of 1-20.

The symmetrical aromatic tetracarboxylic acid anhydride represented by the above general formula can be exemplified: 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenyl tetracarboxylic acid Acid dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, 4,4'-[ Propane-2,2-diylbis(1,4-phenyleneoxy))bisphthalic dianhydride, 2,2-bis(3,3',4,4'-tetracarboxyphenyl) Tetrafluoropropane dianhydride, 2,2-bis(3,4-dicarboxyphenyl) propane dianhydride, 2,2'-bis(3,4-dicarboxyphenoxyphenyl) dianhydride, 2, 2',3,3'-Biphenyltetracarboxylic dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, pyromellitic dianhydride, 1,2,3,4- Pyromellitic anhydride, 1,4,5,8-naphthalenetetracarboxylic anhydride, 2,3,6,7-naphthalenetetracarboxylic anhydride, etc.

Among the above-mentioned symmetrical aromatic tetracarboxylic acid anhydrides, from the viewpoints of compatibility between aromatic tetracarboxylic acid anhydride and diamine, room temperature adhesion, and heat resistance adhesion, it is preferably selected from 3, 3', 4, 4' -Benzophenone tetracarboxylic dianhydride, 4,4'-[propane-2,2-diylbis(1,4-phenyleneoxy)]bisphthalic dianhydride and 4,4' -At least one of the group consisting of oxybisphthalic anhydride.

The upper limit of the content of symmetrical aromatic tetracarboxylic acid anhydride in 100 mol% of aromatic tetracarboxylic acid anhydride can be exemplified: 100 mol%, 90 mol%, 80 mol%, 70 mol%, 60 mol%, 55 mol%, 50 mol%, 40 mol%, 30 mol%, 20 mol%, 10 mol%, etc.; the lower limit can be exemplified: 95 mol%, 90 mol%, 80 mol%, 70 mol%, 60 mol%, 50 mol%, 40 mol%, 30 mol%, 20 mol%, 10 mol%, 0 mol%, etc. In one embodiment, the content of the symmetrical aromatic tetracarboxylic acid anhydride in 100 mol% of the aromatic tetracarboxylic acid anhydride is preferably about 50 to 100 mol%.

The upper limit of the content of the symmetric aromatic tetracarboxylic anhydride in 100% by mass of aromatic tetracarboxylic anhydride can be exemplified: 100% by mass, 90% by mass, 80% by mass, 70% by mass, 60% by mass, 55% by mass, and 50% by mass %, 40% by mass, 30% by mass, 20% by mass, 10% by mass, etc.; the lower limit can be exemplified: 95% by mass, 90% by mass, 80% by mass, 70% by mass, 60% by mass, 50% by mass, 40% by mass , 30% by mass, 20% by mass, 10% by mass, 0% by mass, etc. In one embodiment, the content of the symmetrical aromatic tetracarboxylic anhydride in 100% by mass of the aromatic tetracarboxylic anhydride is preferably about 0-100% by mass, more preferably about 50-100% by mass.

The upper limit of the content of the symmetrical aromatic tetracarboxylic acid anhydride in 100 mol% of the monomer group can be exemplified: 75 mol%, 70 mol%, 60 mol%, 50 mol%, 40 mol%, 30 Mole%, 20 Mole%, 10 Mole%, 5 Mole%, etc.; the lower limit can be exemplified: 70 Mole%, 60 Mole%, 50 Mole%, 40 Mole%, 30 Mole%, 20 Mole%, 10 Mole%, 5 Mole%, 0 Mole%, etc. In one embodiment, the content of the symmetrical aromatic tetracarboxylic acid anhydride in 100 mol% of the monomer group is preferably about 0 to 75 mol%.

The upper limit of the content of the symmetrical aromatic tetracarboxylic anhydride in 100% by mass of the monomer group can be exemplified: 75% by mass, 70% by mass, 60% by mass, 50% by mass, 40% by mass, 30% by mass, and 20% by mass , 10% by mass, 5% by mass, etc.; the lower limit can be exemplified: 70% by mass, 60% by mass, 50% by mass, 40% by mass, 30% by mass, 20% by mass, 10% by mass, 5% by mass, 0% by mass, etc. . In one embodiment, the content of the symmetrical aromatic tetracarboxylic anhydride in 100% by mass of the monomer group is preferably about 0 to 75% by mass.

(Other aromatic tetracarboxylic anhydrides) In one embodiment, the monomer group may include aromatic tetracarboxylic anhydrides (also referred to as Other aromatic tetracarboxylic anhydrides).

In one embodiment, the content of other acid anhydrides in the aromatic tetracarboxylic acid anhydride can be exemplified: less than 5 mol%, less than 4 mol%, less than 1 mol%, less than 0.9 mol%, Less than 0.5 mol%, less than 0.1 mol%, about 0 mol%, etc.

In one embodiment, the content of other acid anhydrides in the aromatic tetracarboxylic anhydride can be exemplified: less than 5 mass%, less than 4 mass%, less than 1 mass%, less than 0.9 mass%, and less than 0.5 mass% %, less than 0.1% by mass, about 0% by mass, etc.

In one embodiment, the content of other acid anhydrides in the monomer group can be exemplified: less than 5 mol%, less than 4 mol%, less than 1 mol%, less than 0.9 mol%, low At 0.5 mol%, less than 0.1 mol%, 0 mol%, etc.

In one embodiment, the content of other acid anhydrides in the monomer group can be exemplified: less than 5% by mass, less than 4% by mass, less than 1% by mass, less than 0.9% by mass, and less than 0.5% by mass , Less than 0.1% by mass, about 0% by mass, etc.

The upper limit of the content of aromatic tetracarboxylic anhydride in 100 mol% of the monomer group can be exemplified: 75 mol%, 70 mol%, 65 mol%, 60 mol%, 55 mol%, etc.; the lower limit Examples include: 70 mol%, 65 mol%, 60 mol%, 55 mol%, 50 mol%, etc. In one embodiment, the content of the aromatic tetracarboxylic anhydride in 100 mol% of the monomer group is preferably about 50 to 75 mol%.

The upper limit of the content of aromatic tetracarboxylic anhydride in 100% by mass of the monomer group can be exemplified: 75% by mass, 70% by mass, 65% by mass, 60% by mass, 55% by mass, etc.; the lower limit can be exemplified: 70% by mass , 65% by mass, 60% by mass, 55% by mass, 50% by mass, etc. In one embodiment, the content of the aromatic tetracarboxylic anhydride in 100% by mass of the monomer group is preferably about 50 to 75% by mass.

<Diamine> Diamine can be used singly or in two or more types. Examples of diamines include dimer diamines, diamines containing a sulphur skeleton, and diamine-based polysiloxanes.

(Dimer diamine) In the present invention, dimer diamine refers to a dimer of unsaturated fatty acid such as oleic acid, that is, a substance obtained by substituting all the carboxyl groups of the dimer acid with primary amine groups (refer to Japanese Japanese Patent Application Laid-Open No. 9-12712 etc.), various known dimer diamines can be used without particular limitation. Below, the non-limiting general formula of dimer diamine is shown (in each formula, m+n=6-17, preferably p+q=8-19, and the dotted line represents a carbon-carbon single bond Or carbon-carbon double bond).

Commercial products of dimer diamines can be exemplified: Versamine 551 (manufactured by Corning Co., Ltd.), Versamine 552 (manufactured by Corning Co., Ltd.; hydride of Versamine 551), PRIAMINE 1075, and PRIAMINE 1074 (all of which are in Japan Kolloda Co., Ltd.) and so on.

The upper limit of the content of the dimer diamine component in the diamine 100 mol% can be exemplified: 100 mol%, 90 mol%, 80 mol%, 70 mol%, 60 mol%, 50 mol% %, 40 mol%, 30 mol%, 25 mol%, etc.; the lower limit can be exemplified: 90 mol%, 80 mol%, 75 mol%, 70 mol%, 60 mol%, 50 mol% %, 40 mol%, 30 mol%, 25 mol%, 20 mol%, etc. In one embodiment, from the viewpoint of improving flexibility, adhesiveness, and solvent solubility, the content of the dimer diamine component in 100 mol% of diamine is preferably about 20 to 100 mol%.

The upper limit of the content of the dimer diamine component in 100% by mass of diamine can be exemplified: 100% by mass, 90% by mass, 80% by mass, 70% by mass, 60% by mass, 50% by mass, 40% by mass, 30 Mass%, 25% by mass, etc.; the lower limit can be exemplified: 90% by mass, 80% by mass, 75% by mass, 70% by mass, 60% by mass, 50% by mass, 40% by mass, 30% by mass, 25% by mass, 20% by mass %Wait. In one embodiment, from the viewpoint of improving flexibility, adhesiveness, and solvent solubility, the content of the dimer diamine component in 100% by mass of diamine is preferably about 20 to 100% by mass.

The upper limit of the content of the dimer diamine in 100 mol% of the monomer group can be exemplified: 50 mol%, 40 mol%, 30 mol%, 20 mol%, 10 mol%, 8 mol% Ear%, etc.; the lower limit can be exemplified: 40 mol%, 30 mol%, 20 mol%, 10 mol%, 8 mol%, 5 mol%, etc. In one embodiment, the content of dimer diamine in 100 mole% of the monomer group is preferably 5-50 mole%.

The upper limit of the content of the dimer diamine in 100% by mass of the monomer group can be exemplified: 50% by mass, 40% by mass, 30% by mass, 20% by mass, 10% by mass, 8% by mass, etc.; the lower limit can be exemplified : 40% by mass, 30% by mass, 20% by mass, 10% by mass, 8% by mass, 5% by mass, etc. In one embodiment, the content of dimer diamine in 100% by mass of the monomer group is preferably 5-50% by mass.

式中，R¹ 和R² 中的任一個表示具有胺基之基團，另一個表示氫原子、羥基、烷基或鹵素原子，R³ 和R⁴ 中的任一個表示具有胺基之基團，另一個表示氫原子、羥基、烷基或鹵素原子。(Diamine containing a sulphur skeleton) In one of the embodiments, the diamine containing a sulphur skeleton is represented by the following general formula:

In the formula, ^{any one of R 1} and R ² represents a group having an amine group, the other represents a hydrogen atom, a hydroxyl group, an alkyl group or a halogen atom, ^{and any one of R 3} and R ⁴ represents a group having an amine group , The other represents a hydrogen atom, a hydroxyl group, an alkyl group or a halogen atom.

In the present disclosure, "a group having an amino group" means a group obtained by substituting at least one hydrogen atom in an amino group and a functional group with an amino group. Examples of the group having an amino group include an amino group, an alkylamino group, an arylamino group, an alkoxyamino group, and an aryloxyamino group.

The aryl group can be exemplified by a monocyclic aryl group, a condensed ring aryl group, and the like. In addition, one or more hydrogen atoms of the aryl group may be substituted by a linear or branched alkyl group.

Examples of monocyclic aryl groups include phenyl, tolyl, mesityl and the like. In addition, examples of the condensed ring aryl group include naphthyl and the like.

Examples of diamines containing stilbene skeleton include: 9,9'-bis(aminophenyl) sulphur, 9,9'-bis(4-amino-3-methylphenyl) sulphur, 9,9'- Bis(4-amino-3-fluorophenyl)sulfuric acid, 9,9'-bis(4-amino-3-hydroxyphenyl)sulfuric acid, 9,9'-bis(4-methyl-3-amine Phenyl) pyrene, 9,9'-bis(4-fluoro-3-aminophenyl) pyrene, 9,9'-bis(4-hydroxy-3-aminophenyl) pyrene, 9,9' -Bis[4-(4-aminophenoxy)phenyl]茀 and the like.

The upper limit of the content of the diamine-containing diamine component in 100 mole% of diamine can be exemplified: 80 mole%, 70 mole%, 60 mole%, 50 mole%, 40 mole%, 30 mole% Ear%, 25 mol%, etc.; the lower limit can be exemplified: 75 mol%, 70 mol%, 60 mol%, 50 mol%, 40 mol%, 30 mol%, 25 mol%, 20 mol% Ear% etc. In one embodiment, from the viewpoint of improving the dielectric properties, the content of the diamine-containing diamine component in 100 mol% of diamine is preferably about 20 to 80 mol%.

The upper limit of the content of the diamine component containing the quince skeleton in 100% by mass of diamine can be exemplified: 80% by mass, 70% by mass, 60% by mass, 50% by mass, 40% by mass, 30% by mass, 25% by mass, etc. The lower limit can be exemplified: 75% by mass, 70% by mass, 60% by mass, 50% by mass, 40% by mass, 30% by mass, 25% by mass, 20% by mass, etc. In one of the embodiments, from the viewpoint of improving the dielectric properties, the content of the diamine-containing diamine component in 100 mole% of diamine is preferably about 20 to 80% by mass.

The upper limit of the content of the diamine containing the stilbene skeleton in 100 mol% of the monomer group can be exemplified: 50 mol%, 40 mol%, 30 mol%, 20 mol%, 10 mol%, 5 Mole%, etc.; the lower limit can be exemplified: 40 mol%, 30 mol%, 20 mol%, 10 mol%, 5 mol%, 0 mol%, etc. In one of the embodiments, the content of the diamine containing the stilbene skeleton in 100 mol% of the monomer group is preferably 0-50 mol%.

The upper limit of the content of the diamine-containing diamine in 100% by mass of the monomer group can be exemplified: 50% by mass, 40% by mass, 30% by mass, 20% by mass, 10% by mass, 5% by mass, etc.; the lower limit may be Examples: 40% by mass, 30% by mass, 20% by mass, 10% by mass, 5% by mass, 0% by mass, etc. In one of the embodiments, the content of the diamine containing the stilbene skeleton in 100% by mass of the monomer group is preferably 0-50% by mass.

The upper limit of the ratio of the substance amount of the diamine containing the stilbene skeleton to the substance amount of the dimer diamine (the diamine containing the stilbene skeleton/dimer diamine) can be exemplified: 4.00, 3.00, 2.00, 1.00, 0.50, etc. ; The lower limit can be exemplified: 4.00, 3.00, 2.00, 1.00, 0.50, 0.25, etc. In one of the embodiments, from the viewpoint of improving flexibility, adhesiveness, and dielectric properties, the ratio of the amount of diamine-containing diamine to the amount of dimer diamine (diamine-containing diamine) /Dimer diamine), preferably about 0.25 to 4.00.

(Diaminopolysiloxane) Diaminopolysiloxane, for example: α,ω-bis(2-aminoethyl)polydimethylsiloxane, α,ω-bis(3-amine Propyl) polydimethylsiloxane, α,ω-bis(4-aminobutyl)polydimethylsiloxane, α,ω-bis(5-aminopentyl)polydimethylsiloxane Silicone, α,ω-bis[3-(2-aminophenyl)propyl] polydimethylsiloxane, α,ω-bis[3-(4-aminophenyl)propyl] Polydimethylsiloxane, 1,3-bis(3-aminopropyl)tetramethyldisiloxane, 1,3-bis(4-aminobutyl)tetramethyldisiloxane, etc. .

The upper limit of the content of diamine-based polysiloxane in 100 mol% of diamine can be exemplified: 5 mol%, 4 mol%, 3 mol%, 2 mol%, 1 mol%, etc.; the lower limit Examples can be: 4 mol%, 3 mol%, 2 mol%, 1 mol%, 0 mol%, etc. In one embodiment, from the viewpoint of improving flexibility, the content of diaminopolysiloxane in 100 mol% of diamine is preferably about 0 to 5 mol%.

The upper limit of the diamine polysiloxane content in 100% by mass of diamine can be exemplified: 5 mass%, 4% by mass, 3% by mass, 2% by mass, 1% by mass, etc.; the lower limit can be exemplified: 4% by mass , 3% by mass, 2% by mass, 1% by mass, 0% by mass, etc. In one embodiment, from the viewpoint of improving flexibility, the content of diaminopolysiloxane in 100% by mass of diamine is preferably about 0 to 5% by mass.

The upper limit of the content of the diamino polysiloxane in 100 mol% of the monomer group can be exemplified: 5 mol%, 4 mol%, 3 mol%, 2 mol%, 1 mol%, etc. ; The lower limit can be exemplified: 4 mol%, 3 mol%, 2 mol%, 1 mol%, 0 mol%, etc. In one embodiment, from the viewpoint of improving flexibility, the content of diaminopolysiloxane in 100 mol% of the monomer group is preferably about 0 to 5 mol%.

The upper limit of the content of the diaminopolysiloxane in 100% by mass of the monomer group can be exemplified: 5 mass%, 4% by mass, 3% by mass, 2% by mass, 1% by mass, etc.; the lower limit can be exemplified: 4 Mass%, 3% by mass, 2% by mass, 1% by mass, 0% by mass, etc. In one of the embodiments, from the viewpoint of improving flexibility, the content of diaminopolysiloxane in 100% by mass of the monomer group is preferably about 0 to 5% by mass.

(Other diamines) In one embodiment, the monomer group may contain diamines other than the above (also referred to as other diamines). Other diamines can be exemplified: alicyclic diamine, diaminophenoxyphenylpropane, diaminodiphenyl ether, phenylenediamine, diaminodiphenyl sulfide, diaminodiphenyl Diamino benzophenone, diamino diphenyl methane, diamino phenyl propane, diamino phenyl hexafluoropropane, diamino phenyl ethane, diamino phenoxy Benzene, bisaminobenzylbenzene, bisaminodimethylbenzylbenzene, bisaminobistrifluoromethylbenzylbenzene, aminophenoxybiphenyl, aminophenoxyphenyl Ketone, aminophenoxyphenyl sulfide, aminophenoxyphenyl sulfide, aminophenoxyphenyl ether, aminophenoxyphenylpropane, bis(aminophenoxybenzyl) )Benzene, bis(aminophenoxy-α,α-dimethylbenzyl)benzene, bis[(aminoaryloxy)benzyl]diphenyl ether, bis(amino-α ,α-Dimethylbenzylphenoxy)benzophenone, bis[amino-α,α-dimethylbenzylphenoxy]diphenyl sulfide, 4,4'-bis(amine Phenoxyphenoxy]diphenyl sulfide, diaminodiaryloxybenzophenone, diaminoaryloxybenzophenone, 6,6'-bis(aminoaryloxy Group)-3,3,3',3'-tetramethyl-1,1'-spirobisindan, bis(aminoalkyl)ether, bis(aminoalkoxyalkyl)ether, bis( Aminoalkoxy)alkanes, bis[(aminoalkoxy)alkoxy]alkanes, (poly)ethylene glycol bis(aminoalkyl)ether, bis(aminoaryloxy)pyridine, Alkyl diamine and so on.

Alicyclic diamines can be exemplified: diaminocyclohexane, diaminodicyclohexylmethane, dimethyldiaminodicyclohexylmethane, diaminobicyclo[2.2.1]heptane, bis(amine Methyl)bicyclo[2.2.1]heptane, 3(4),8(9)-bis(aminomethyl)tricyclo[5.2.1.02,6]decane, isophoronediamine, 4 ,4'-Diaminodicyclohexylmethane and 1,3-diaminomethylcyclohexane, etc.

Bisaminophenoxyphenylpropane, exemplified by: 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)基)phenyl]propane and the like.

Diaminodiphenyl ether, for example: 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, etc. .

Examples of phenylenediamine include phenylenediamines such as p-phenylenediamine and m-phenylenediamine.

Diaminodiphenyl sulfide, for example: 3,3'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl Base sulfide and so on.

Examples of diamino diphenyl ingots: 3,3'-diamino diphenyl ingots, 3,4'-diamino diphenyl ingots, 4,4'-diamino diphenyl ingots, etc. .

Diaminobenzophenone, exemplified: 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, etc. .

Diaminodiphenylmethane, exemplified: 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, etc. .

Examples of diaminophenylpropane include: 2,2-bis(3-aminophenyl)propane, 2,2-bis(4-aminophenyl)propane, 2-(3-aminophenyl) -2-(4-aminophenyl)propane and the like.

Examples of diaminophenyl hexafluoropropane include: 2,2-bis(3-aminophenyl)-1,1,1,3,3,3-hexafluoropropane, 2,2-bis(4- Aminophenyl)-1,1,1,3,3,3-hexafluoropropane, 2-(3-aminophenyl)-2-(4-aminophenyl)-1,1,1, 3,3,3-hexafluoropropane, etc.

Diaminophenyl phenyl ethane can be exemplified: 1,1-bis(3-aminophenyl)-1-phenylethane, 1,1-bis(4-aminophenyl)-1- Phenylethane, 1-(3-aminophenyl)-1-(4-aminophenyl)-1-phenylethane, etc.

Bisaminophenoxybenzene, exemplified by 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(3 -Aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, etc.

Bisaminobenzylbenzene, exemplified by 1,3-bis(3-aminobenzyl)benzene, 1,3-bis(4-aminobenzyl)benzene, 1,4- Bis(3-aminobenzyl)benzene, 1,4-bis(4-aminobenzyl)benzene, etc.

Bisaminodimethylbenzylbenzene, exemplified by: 1,3-bis(3-amino-α,α-dimethylbenzyl)benzene, 1,3-bis(4-amino-α ,α-dimethylbenzyl)benzene, 1,4-bis(3-amino-α,α-dimethylbenzyl)benzene, 1,4-bis(4-amino-α,α -Dimethylbenzyl)benzene and the like.

Bisaminobis(trifluoromethyl)benzylbenzene, exemplified by 1,3-bis(3-amino-α,α-bistrifluoromethylbenzyl)benzene, 1,3-bis(4- Amino-α,α-bistrifluoromethylbenzyl)benzene, 1,4-bis(3-amino-α,α-bistrifluoromethylbenzyl)benzene, 1,4-bis( 4-Amino-α,α-bistrifluoromethylbenzyl)benzene and the like.

Examples of aminophenoxybiphenyl include: 2,6-bis(3-aminophenoxy)benzonitrile, 4,4'-bis(3-aminophenoxy)biphenyl, 4,4 '-Bis(4-aminophenoxy)biphenyl and the like.

Examples of the aminophenoxyphenyl ketone include bis[4-(3-aminophenoxy)phenyl]ketone, bis[4-(4-aminophenoxy)phenyl]ketone, and the like.

Aminophenoxyphenyl sulfide, for example: bis[4-(3-aminophenoxy)phenyl]sulfide, bis[4-(4-aminophenoxy)phenyl]sulfide Wait.

Examples of the aminophenoxyphenyl ash include bis[4-(3-aminophenoxy)phenyl] ash, bis[4-(4-aminophenoxy)phenyl] ash, and the like.

Examples of the aminophenoxyphenyl ether include bis[4-(3-aminophenoxy)phenyl]ether, bis[4-(4-aminophenoxy)phenyl]ether, and the like.

Examples of aminophenoxyphenylpropane include: 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 2,2-bis[3-(3-aminophenoxy) )Phenyl]-1,1,1,3,3,3-hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3, 3,3-hexafluoropropane and so on.

Bis(aminophenoxybenzyl)benzene can be exemplified: 1,3-bis[4-(3-aminophenoxy)benzyl]benzene, 1,3-bis[4-( 4-aminophenoxy)benzyl]benzene, 1,4-bis[4-(3-aminophenoxy)benzyl]benzene, 1,4-bis[4-(4- Aminophenoxy)benzyl]benzene and the like.

Bis(aminophenoxy-α,α-dimethylbenzyl)benzene, for example: 1,3-bis[4-(3-aminophenoxy)-α,α-dimethylbenzene Methyl]benzene, 1,3-bis[4-(4-aminophenoxy)-α,α-dimethylbenzyl]benzene, 1,4-bis[4-(3-aminobenzene) Oxy)-α,α-dimethylbenzyl]benzene, 1,4-bis[4-(4-aminophenoxy)-α,α-dimethylbenzyl]benzene, etc.

Bis[(aminoaryloxy)benzyl]diphenyl ether, for example: 4,4'-bis[4-(4-aminophenoxy)benzyl]diphenyl ether Wait.

Bis(amino-α,α-dimethylbenzylphenoxy)benzophenone, for example: 4,4'-bis[4-(4-amino-α,α-dimethylbenzene (Methyl)phenoxy]benzophenone and the like.

Bis[amino-α,α-dimethylbenzylphenoxy]diphenyl sulfide, for example: 4,4'-bis[4-(4-amino-α,α-dimethylbenzene Methyl)phenoxy]diphenyl sulfide and the like.

4,4'-bis[aminophenoxyphenoxy]diphenyl sulfide, for example: 4,4'-bis[4-(4-aminophenoxy)phenoxy]diphenyl sulfide Wait.

Diaminodiaryloxybenzophenone, exemplified by: 3,3'-diamino-4,4'-diphenoxybenzophenone, 3,3'-diamino-4, 4'-Dibiphenoxybenzophenone, etc.

Diaminoaryloxybenzophenone, exemplified: 3,3'-diamino-4-phenoxybenzophenone, 3,3'-diamino-4-biphenoxydi Benzophenone and so on.

6,6'-bis(aminoaryloxy)-3,3,3',3'-tetramethyl-1,1'-spirobisindan, for example: 6,6'-bis(3 -Aminophenoxy)-3,3,3',3'-tetramethyl-1,1'-spirobisindan, 6,6'-bis(4-aminophenoxy)-3, 3,3',3'-tetramethyl-1,1'-spirobisindan, etc.

Examples of the bis(aminoalkyl)ether include bis(aminomethyl)ether, bis(2-aminoethyl)ether, and bis(3-aminopropyl)ether.

Bis (amino alkoxy alkyl) ether, exemplified: bis [2-(amino methoxy) ethyl] ether, bis [2-(2-aminoethoxy) ethyl] ether, bis [2-(3-Aminopropoxy)ethyl]ether and the like.

Examples of bis(aminoalkoxy)alkanes include 1,2-bis(aminomethoxy)ethane, 1,2-bis(2-aminoethoxy)ethane, and the like.

Bis[(aminoalkoxy)alkoxy]alkanes, exemplified by 1,2-bis[2-(aminomethoxy)ethoxy]ethane, 1,2-bis[2-(2 -Aminoethoxy)ethoxy]ethane and the like.

(Poly)ethylene glycol bis(aminoalkyl) ether, exemplified by: ethylene glycol bis(3-aminopropyl) ether, diethylene glycol bis(3-aminopropyl) ether, triethylenedi Alcohol bis(3-aminopropyl) ether and the like.

Examples of bis(aminoaryloxy)pyridine include 2,6-bis(3-aminophenoxy)pyridine and the like.

Alkylene diamine, exemplified: ethylene diamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexyl Alkane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminodecane Monoalkane, 1,12-diaminododecane, etc.

In one of the embodiments, the content of other diamines in the diamine can be exemplified: less than 5 mol%, less than 4 mol%, less than 1 mol%, less than 0.9 mol%, and less than 0.5 mol%, less than 0.1 mol%, about 0 mol%, etc.

In one embodiment, the content of other diamines in the diamine can be exemplified: less than 5% by mass, less than 4% by mass, less than 1% by mass, less than 0.9% by mass, less than 0.5% by mass, Less than 0.1% by mass, about 0% by mass, etc.

In one of the embodiments, the content of other diamines in the monomer group can be exemplified: less than 5 mol%, less than 4 mol%, less than 1 mol%, less than 0.9 mol%, Less than 0.5 mol%, less than 0.1 mol%, about 0 mol%, etc.

In one of the embodiments, the content of other diamines in the monomer group can be exemplified: less than 5% by mass, less than 4% by mass, less than 1% by mass, less than 0.9% by mass, and less than 0.5% by mass. %, less than 0.1% by mass, about 0% by mass, etc.

The upper limit of the content of diamine in 100 mol% of the monomer group can be exemplified: 50 mol%, 45 mol%, 40 mol%, 35 mol%, 30 mol%, etc.; the lower limit can be exemplified: 45 mol%, 40 mol%, 35 mol%, 30 mol%, 25 mol%, etc. In one of the embodiments, the content of diamine in 100 mol% of the monomer group is preferably about 25-50 mol%.

The upper limit of the diamine content in 100% by mass of the monomer group can be exemplified: 50% by mass, 45% by mass, 40% by mass, 35% by mass, 30% by mass, etc.; the lower limit can be exemplified: 45% by mass, 40% by mass %, 35% by mass, 30% by mass, 25% by mass, etc. In one embodiment, the content of diamine in 100% by mass of the monomer group is preferably about 25-50% by mass.

The upper limit of the molar ratio of aromatic tetracarboxylic anhydride to diamine [aromatic tetracarboxylic anhydride/diamine] can be exemplified: 1.5, 1.4, 1.3, 1.2, 1.1, etc.; the lower limit can be exemplified: 1.4, 1.3, 1.2, 1.1 , 1.0, etc. In one embodiment, the molar ratio of aromatic tetracarboxylic anhydride to diamine [aromatic tetracarboxylic anhydride/diamine] is preferably about 1.0 to 1.5 from the viewpoint of solvent solubility and solution stability.

The upper limit of the mass ratio of aromatic tetracarboxylic anhydride to diamine [aromatic tetracarboxylic anhydride/diamine] can be exemplified: 1.5, 1.4, 1.2, 1.0, 0.9, 0.7, 0.6, etc.; the lower limit can be exemplified: 1.4, 1.2, 1.0, 0.9, 0.7, 0.6, 0.5, etc. In one embodiment, the mass ratio of aromatic tetracarboxylic anhydride to diamine [aromatic tetracarboxylic anhydride/diamine] is preferably 0.5 to 1.5.

<Other monomers> In one of the embodiments, the monomer group may include monomers that are neither aromatic tetracarboxylic anhydride nor diamine (also referred to as other monomers). Examples of other monomers include aliphatic tetracarboxylic anhydride and the like.

In one embodiment, the content of other monomers in the monomer group can be exemplified: less than 5 mol%, less than 4 mol%, less than 1 mol%, less than 0.9 mol%, Less than 0.5 mol%, less than 0.1 mol%, about 0 mol%, etc.

In one embodiment, the content of other monomers in the monomer group can be exemplified: less than 5% by mass, less than 4% by mass, less than 1% by mass, less than 0.9% by mass, and less than 0.5% by mass. %, less than 0.1% by mass, about 0% by mass, etc.

<Physical properties of polyimine, etc.> The upper limit of the weight average molecular weight of the polyimine can be exemplified: 50000, 40000, 30000, 20000, 10000, 7500, 5500, etc.; the lower limit can be exemplified: 45000, 40000, 30000, 20000 , 10000, 7500, 5000, etc. In one embodiment, the weight average molecular weight of the polyimide is preferably 5,000 to 50,000 from the viewpoint of dielectric properties, solvent solubility, and flexibility.

The upper limit of the number average molecular weight of the polyimide can be exemplified: 40000, 30000, 20000, 10000, 7500, 5000, 3000, etc.; the lower limit can be exemplified: 35000, 30000, 20000, 10000, 7500, 5000, 3000, 2000, etc. . In one embodiment, from the viewpoint of dielectric properties, solvent solubility, and flexibility, the number average molecular weight of the polyimide is preferably 2,000 to 40,000.

The weight average molecular weight and the number average molecular weight can be determined as a value in terms of polystyrene measured by gel permeation chromatography (GPC), for example.

The upper limit of the softening point of the polyimide can be exemplified: 220°C, 200°C, 150°C, 100°C, 50°C, 25°C, etc.; the lower limit can be exemplified: 210°C, 200°C, 150°C, 100°C, 50 ℃, 25℃, 20℃, etc. In one of the embodiments, from the viewpoints of workability, heat resistance, and solvent solubility, the softening point of the polyimide is preferably 20 to 220°C.

The softening point can be obtained using a commercially available measuring instrument ("ARES-2KSTD-FCO-STD" manufactured by Rheometric Scientfic) or the like.

<The manufacturing method etc. of polyimide> The said polyimide can be manufactured by various well-known methods. The production method of polyimide can be exemplified: a method including the following steps: making a monomer group containing diamines such as aromatic tetracarboxylic anhydrides and dimer diamines, preferably 60 to 120 The polyaddition reaction is carried out at a temperature of about ℃, more preferably about 80-100 ℃, preferably about 0.1 to 2 hours, more preferably about 0.1 to 0.5 hours, to obtain a polyadduct; The resulting product is preferably subjected to the imidization reaction, that is, the dehydration ring-closing reaction, at a temperature of preferably about 80 to 250°C, more preferably about 100 to 200°C, preferably about 0.5 to 50 hours, more preferably 1 to About 20 hours.

In addition, in the step of performing the imidization reaction, various known reaction catalysts, dehydrating agents, and organic solvents described later can be used. Various known reaction catalysts, dehydrating agents, and organic solvents described later can be used alone or in two or more types. Examples of the reaction catalyst include aliphatic tertiary amines such as triethylamine; aromatic tertiary amines such as dimethylaniline; heterocyclic tertiary amines such as pyridine, picoline, and isoquinoline. In addition, examples of the dehydrating agent include aliphatic acid anhydrides such as acetic anhydride and aromatic acid anhydrides such as benzoic anhydride.

The ring-closure rate of the polyimine is not particularly limited. Here, "imine ring closure rate" means the content of the cyclic imine bond in the polyimine, which can be determined by various spectroscopic means such as nuclear magnetic resonance (NMR) or infrared (IR) analysis. In addition, from the viewpoint of making room-temperature adhesiveness and heat-resistant adhesiveness good, the imine ring closure rate of the polyimide is preferably about 70% or more, and more preferably about 85 to 100%.

[Adhesive] The present disclosure provides an adhesive including the above-mentioned polyimide, a crosslinking agent and an organic solvent.

The upper limit of the content of the polyimide in 100% by mass of the adhesive can be exemplified: 90% by mass, 80% by mass, 70% by mass, 60% by mass, 50% by mass, 40% by mass, 30% by mass, 20 Mass%, 10% by mass, etc.; the lower limit can be exemplified: 80% by mass, 70% by mass, 60% by mass, 50% by mass, 40% by mass, 30% by mass, 20% by mass, 10% by mass, 5% by mass, etc. The content of the polyimide in 100% by mass of the adhesive is preferably about 5 to 90% by mass.

<Crosslinking agent> As long as the crosslinking agent can function as a crosslinking agent of polyimine, various well-known crosslinking agents can be used without a restriction|limiting in particular. The crosslinking agent can be used alone or in two or more types. The crosslinking agent is preferably at least one selected from the group consisting of epoxides, benzoxazines, bismaleimides, and cyanate esters.

(Epoxide) Epoxides can be exemplified: phenol novolak type epoxide, cresol novolak type epoxide, bisphenol A type epoxide, bisphenol F type epoxide, bisphenol S type epoxide Oxide, hydrogenated bisphenol A type epoxide, hydrogenated bisphenol F type epoxide, stilbene type epoxide, epoxide containing triazine skeleton, epoxide containing stilbene skeleton, linear Aliphatic epoxides, alicyclic epoxides, glycidylamine epoxides, trisphenol methane epoxides, alkyl modified trisphenol methane epoxides, biphenyl epoxy Compounds, epoxides containing dicyclopentadiene skeletons, epoxides containing naphthalene skeletons, aryl alkylene epoxides, tetraglycidyl xylylene diamine, dimer acids of the above epoxides Modifications are dimer acid modified epoxides, dimer acid diglycidyl esters and the like. In addition, examples of commercially available epoxides include: "jER828", "jER834", and "jER807" manufactured by Mitsubishi Chemical Corporation; "ST-3000" manufactured by Nippon Steel Chemical Co., Ltd.; Daicel Chemical "CELLOXIDE 2021P" manufactured by Industrial Co., Ltd.; "YD-172-X75" manufactured by Nippon Steel Chemical Co., Ltd.; "TETRAD-X" manufactured by Mitsubishi Gas Chemical Co., Ltd., etc. Among them, from the viewpoint of the balance of heat resistance, moisture absorption solder heat resistance, and low dielectric properties, it is preferably selected from the group consisting of bisphenol A type epoxides, bisphenol F type epoxides, and hydrogenated bisphenol A type epoxides. At least one of the group consisting of epoxides and alicyclic epoxides.

上述式中，Y表示伸苯基或伸環己基。In particular, the tetraglycidyl diamine having the following structure has good compatibility with the polyimide. In addition, when this component is used, the adhesive layer becomes easy to have a low-loss elastic modulus, and its heat-resistant adhesiveness and low-dielectric properties also become good.

In the above formula, Y represents phenylene or cyclohexylene.

When an epoxy is used as a crosslinking agent, various known hardeners for epoxy can be used in combination. The hardener for epoxides can be used singly or in two or more types. Examples of hardeners for epoxides include succinic anhydride, phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride Dicarboxylic anhydride, 4-methylhexahydrophthalic anhydride, or a mixture of 4-methylhexahydrophthalic anhydride and hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyl tetrahydrophthalic anhydride Hydrogen phthalic anhydride, nadic anhydride, methyl nadic anhydride, norbornane-2,3-dicarboxylic anhydride, methyl norbornane-2,3-dicarboxylic anhydride, methyl ring Anhydride hardeners such as hexene dicarboxylic anhydride, 3-dodecenyl succinic anhydride, and octenyl succinic anhydride; dicyandiamide (DICY), aromatic diamines (trade names "LonzacureM-DEA", "LonzacureM-DETDA" "Etc., all manufactured by Lonza Japan Co., Ltd.), aliphatic amines and other amine hardeners; phenol novolak resin, cresol novolak resin, bisphenol A novolak resin, triazine-modified phenol novolak resin, Phenolic hardeners such as phosphazene containing phenolic hydroxyl group (trade name "SPH-100" manufactured by Otsuka Chemical Co., Ltd.), cyclic phosphazene compounds; maleic acid-modified rosin or its hydride, etc. Rosin-based crosslinking agent, etc. Among them, phenolic hardeners are preferred, and phosphazene hardeners containing phenolic hydroxyl groups are particularly preferred. The amount of the curing agent used is not particularly limited. When the solid content of the adhesive is 100% by mass, it is preferably about 0.1 to 120% by mass, and more preferably about 10 to 40% by mass.

When an epoxy and an epoxy hardener are used in combination as a crosslinking agent, a reaction catalyst may be further used in combination. The reaction catalyst can be used alone or in two or more types. Examples of reaction catalysts include: 1,8-diaza-bicyclo[5.4.0]undecene-7, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, Ginseng (dimethylaminomethyl) phenol and other tertiary amines; 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole and other imidazoles ; Tributyl phosphine, methyl diphenyl phosphine, triphenyl phosphine, diphenyl phosphine, phenyl phosphine and other organic phosphines; tetraphenyl phosphonium tetraphenyl borate, 2-ethyl-4-methyl Tetraphenyl borate such as imidazole tetraphenyl borate, N-methylmorpholine tetraphenyl borate, etc. In addition, the amount of the reaction catalyst used is not particularly limited, but when the solid content of the adhesive is 100% by mass, it is preferably about 0.01 to 5% by mass.

(Benzoxazine) Benzoxazine, exemplified: 6,6-(1-methylethylene)bis(3,4-dihydro-3-phenyl-2H-1,3-benzoxazine) Oxazine), 6,6-(1-methylethylene)bis(3,4-dihydro-3-methyl-2H-1,3-benzoxazine) and the like. Furthermore, a phenyl group, a methyl group, a cyclohexyl group, etc. may be bonded to the nitrogen of the oxazine ring. In addition, commercial products of benzoxazine can be exemplified: "Benzoxazine Fa type" or "benzoxazine Pd type" manufactured by Shikoku Chemical Industry Co., Ltd., and "RLV-100" manufactured by Air Water Corporation. "Wait.

(Bismaleimide) Bismaleimide, exemplified: 4,4'-diphenylmethane bismaleimide, meta-phenyl bismaleimide, bisphenol A diphenyl Base ether bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1, 3-phenylene bismaleimide, 1,6'-bismaleimide-(2,2,4-trimethyl)hexane, 4,4'-diphenyl ether bismaleimide Amide, 4,4'-diphenyl bismaleimide, etc. In addition, as a commercial product of bismaleimide, "BAF-BMI" manufactured by JFE Chemical Co., Ltd. can be exemplified.

(Cyanate ester) Cyanate ester, for example: 2-allylphenol cyanate ester, 4-methoxyphenol cyanate ester, 2,2-bis(4-cyanooxyphenol)-1,1, 1,3,3,3-hexafluoropropane, bisphenol A cyanate, diallyl bisphenol A cyanate, 4-phenylphenol cyanate, 1,1,1-ginseng (4-cyano (Oxyphenyl) ethane, 4-cumyl phenol cyanate, 1,1-bis(4-cyanooxyphenyl) ethane, 4,4'-bisphenol cyanate and 2,2 -Bis(4-cyanooxyphenyl)propane and the like. In addition, as a commercially available product of cyanate ester, "PRIMASET BTP-6020S (manufactured by Lonza Japan Co., Ltd.)" and the like can be exemplified.

In the above-mentioned adhesive, the upper limit of the content of the crosslinking agent relative to 100 parts by mass (calculated as solid content) of the above-mentioned polyimide can be exemplified: 900 parts by mass, 800 parts by mass, 700 parts by mass, 600 parts by mass, 500 parts by mass, 400 parts by mass, 300 parts by mass, 200 parts by mass, 100 parts by mass, 50 parts by mass, 20 parts by mass, 10 parts by mass, etc.; the lower limit can be exemplified: 800 parts by mass, 700 parts by mass, 600 parts by mass, 500 Parts by mass, 400 parts by mass, 300 parts by mass, 200 parts by mass, 100 parts by mass, 50 parts by mass, 20 parts by mass, 10 parts by mass, 5 parts by mass, etc. In one embodiment, the content of the crosslinking agent is preferably about 5 to 900 parts by mass relative to 100 parts by mass (calculated as solid content) of the polyimide.

The upper limit of the content of the crosslinking agent in the above-mentioned adhesive 100% by mass can be exemplified: 80% by mass, 70% by mass, 60% by mass, 50% by mass, 40% by mass, 30% by mass, 20% by mass, and 10% by mass , 5% by mass, etc.; the lower limit can be exemplified: 70% by mass, 60% by mass, 50% by mass, 40% by mass, 30% by mass, 20% by mass, 10% by mass, 5% by mass, 2% by mass, etc. In one embodiment, the content of the crosslinking agent in 100% by mass of the adhesive is preferably about 2 to 80% by mass.

<Organic solvent> The organic solvent can be used alone or in two or more kinds of various well-known organic solvents. Examples of organic solvents include: N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, dimethyl sulfide, N-methylcaprolactam, triethylene glycol dimethyl Aprotic polar solvents such as methyltriglyme and methyldiglyme; or alicyclic solvents such as cyclohexanone and methylcyclohexane; methanol, ethanol, propanol, benzyl alcohol, methyl Alcohol solvents such as phenol; aromatic solvents such as toluene.

In addition, the content of the organic solvent in the adhesive is not particularly limited, but it is preferable that the mass of the solid content be 10 to 60% by mass relative to 100% by mass of the adhesive.

In the above-mentioned adhesive, the upper limit of the content of the organic solvent relative to 100 parts by mass (calculated as solid content) of the above-mentioned polyimide, the upper limit of the content of the organic solvent can be exemplified: 900 parts by mass, 800 parts by mass, 700 parts by mass, 600 parts by mass, 500 parts by mass Parts by mass, 400 parts by mass, 300 parts by mass, 200 parts by mass, etc.; the lower limit can be exemplified: 800 parts by mass, 700 parts by mass, 600 parts by mass, 500 parts by mass, 400 parts by mass, 300 parts by mass, 200 parts by mass, 150 parts by mass Servings and so on. In one embodiment, the content of the organic solvent in the adhesive is preferably 150 to 900 parts by mass relative to 100 parts by mass (calculated as solid content) of the polyimide.

<Flame retardant> In one of the embodiments, the adhesive includes a flame retardant. The flame retardant can be used singly or in two or more types. Examples of flame retardants include phosphorus-based flame retardants, inorganic fillers, and the like.

(Phosphorus-based flame retardant (phosphorus-containing flame retardant)) Phosphorus-based flame retardants can be exemplified by polyphosphoric acid or phosphoric acid ester, phosphazene derivatives without phenolic hydroxyl groups, and the like. Among the phosphazene derivatives, cyclic phosphazene derivatives are preferred from the viewpoints of flame retardancy, heat resistance, bleed-out resistance, and the like. Examples of commercially available cyclic phosphazene derivatives include SPB-100 manufactured by Otsuka Chemical Co., Ltd., Rabitle FP-300B manufactured by Fushimi Pharmaceutical Co., Ltd., and the like.

(Inorganic filler) In one embodiment, the inorganic filler can be exemplified by silica filler, phosphorous filler, fluorine filler, inorganic ion exchanger filler, and the like. Examples of commercially available products include: FB-3SDC manufactured by Denka Co., Ltd., Exolit OP935 manufactured by Clariant Chemical Co., Ltd., KTL-500F manufactured by Kitamura Co., Ltd., IXE manufactured by Toagosei Co., Ltd., and the like.

In the above adhesive, the upper limit of the content of the flame retardant relative to 100 parts by mass (calculated as solid content) of the polyimide can be exemplified: 150 parts by mass, 100 parts by mass, 50 parts by mass, 10 parts by mass, 5 Parts by mass, etc.; the lower limit can be exemplified: 125 parts by mass, 100 parts by mass, 50 parts by mass, 10 parts by mass, 5 parts by mass, 1 part by mass, etc. In one embodiment, in the adhesive, the content of the flame retardant is preferably 1 to 150 parts by mass relative to 100 parts by mass (calculated as solid content) of the polyimide.

<Reactive alkoxysilyl compound> In one of the embodiments, the adhesive further includes the general formula Z-Si(R ¹ ) _a (OR ² ) _3-a (where Z means that it contains an acid anhydride The group of the functional group that the group reacts, R ¹ represents hydrogen or a hydrocarbon group having ^{1 to 8 carbon atoms, R 2} represents a hydrocarbon group having 1 to 8 carbon atoms, and a represents 0, 1, or 2.) represents a reactive alkoxy group. Silicon-based compounds. The use of reactive alkoxysilyl compounds can maintain the low dielectric properties of the adhesive layer composed of the adhesive of the present invention and adjust its melt viscosity. As a result, it is possible to improve the interface adhesion between the adhesive layer and the base material (the so-called anchoring effect) while suppressing the exudation of the hardened layer from the end of the base material.

Examples of the reactive functional group contained in Z in the above general formula include an amino group, an epoxy group, and a thiol group.

Z contains an amino group compound, for example: N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-amino group Propyl trimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-ureidopropyltrialkoxysilane, etc. As the compound in which Z contains an epoxy group, for example, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3 -Glycidoxy propyl trimethoxy silane, 3-glycidoxy propyl methyl diethoxy silane, 3-glycidoxy propyl triethoxy silane, etc. As the compound in which Z contains a thiol group, for example, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and 3-mercaptopropyltrimethoxysilane can be exemplified. Propyl methyl diethoxy silane and so on. Among them, from the viewpoint of reactivity and good flow control effect, a compound in which Z contains an amine group is preferred.

In the above-mentioned adhesive, the upper limit of the content of the reactive alkoxysilyl compound relative to 100 parts by mass (calculated as solid content) of the polyimide can be exemplified: 5 parts by mass, 2.5 parts by mass, 1 part by mass, 0.5 parts by mass, 0.1 parts by mass, 0.05 parts by mass, etc.; the lower limit can be exemplified: 4 parts by mass, 2.5 parts by mass, 1 part by mass, 0.5 parts by mass, 0.1 parts by mass, 0.05 parts by mass, 0.01 parts by mass, etc. In one embodiment, in the adhesive, the content of the reactive alkoxysilyl compound relative to 100 parts by mass (calculated as solid content) of the polyimide is preferably 0.01 to 5 parts by mass.

The above-mentioned adhesive may contain any one of the above-mentioned polyimide, crosslinking agent, organic solvent, flame retardant, and reactive alkoxysilyl compound as an additive.

Examples of additives include: ring-opening esterification reaction catalyst, dehydrating agent, plasticizer, weathering agent, antioxidant, heat stabilizer, lubricant, antistatic agent, brightener, coloring agent, conductive agent, mold release agent , Surface treatment agent, viscosity regulator, silica filler and fluorine filler, etc.

In one embodiment, the content of the additive relative to 100 parts by mass of the adhesive can be exemplified: less than 1 part by mass, less than 0.1 part by mass, less than 0.01 part by mass, 0 part by mass, and the like.

In another embodiment, relative to 100 parts by mass (calculated as solid content) of the polyimide, the content of the additive can be exemplified: less than 1 part by mass, less than 0.1 part by mass, less than 0.01 part by mass, 0 parts by mass, etc.

The above-mentioned adhesive can be obtained by dissolving the above-mentioned polyimide and crosslinking agent, and if necessary, a flame retardant, a reactive alkoxysilyl compound, and additives in an organic solvent.

[Film-shaped adhesive material] The present disclosure provides a film-shaped adhesive material, which includes a heat-cured product of the above-mentioned adhesive. The manufacturing method of the film-like adhesive material can be exemplified by a method including the following steps: the step of applying the above-mentioned adhesive to an appropriate support, the step of curing by volatilizing an organic solvent by heating, Steps on peeling, etc. The thickness of the adhesive material is not particularly limited, but is preferably about 3 μm to 40 μm. The supporting body can be exemplified by the following materials.

[Adhesive layer] The present disclosure provides an adhesive layer, which contains an adhesive or the above-mentioned film-like adhesive material. When manufacturing the said adhesive layer, the said adhesive agent and various well-known adhesive agents other than the said adhesive agent can be used together. Similarly, the above-mentioned film-like adhesive material and various well-known film-like adhesive materials other than the above-mentioned film-like adhesive material may also be used in combination.

[Adhesive Sheet] The present disclosure provides an adhesive sheet including the above-mentioned adhesive layer and a supporting film.

The supporting film can be exemplified by a plastic film. Plastics can be exemplified: polyester, polyimide, polyimide-silica mixture, polyethylene, polypropylene, polyethylene terephthalate, polyethylene naphthalate, polymethyl Methyl acrylate resin, polystyrene resin, polycarbonate resin, acrylonitrile-butadiene-styrene resin, composed of ethylene terephthalate, phenol, phthalic acid, hydroxynaphthoic acid, etc. and p-hydroxybenzene Aromatic polyester resin obtained from formic acid (so-called liquid crystal polymer, "Vecstar" manufactured by Kuraray Co., Ltd., etc.) and the like.

In addition, when applying the above-mentioned adhesive to the support film, the above-mentioned coating means can be used. The thickness of the coating is also not particularly limited, and the thickness after drying is preferably about 1 μm to 100 μm, more preferably about 3 μm to 50 μm. In addition, the adhesive layer of the adhesive sheet can be protected with various protective films.

[Copper foil with resin] The present disclosure provides a copper foil with resin, which includes the above-mentioned adhesive layer and copper foil. Specifically, the above-mentioned resin-attached copper foil is a material obtained by coating or bonding the adhesive or the film-like adhesive material on the copper foil. Examples of this copper foil include rolled copper foil and electrolytic copper foil. The thickness is not particularly limited, but is preferably about 1 μm to 100 μm, more preferably about 2 μm to 38 μm. In addition, the copper foil may be copper foil that has been subjected to various surface treatments (roughening, rust prevention, etc.). The rust-preventing treatment can be exemplified by so-called mirror-finishing treatments such as plating treatment and chromate treatment performed using a plating solution containing nickel (Ni), zinc (Zn), tin (Sn), and the like. In addition, as the coating means, the aforementioned method can be exemplified.

In addition, the adhesive layer of the resin-attached copper foil may be an uncured adhesive layer, and may also be an adhesive layer that is partially hardened or completely hardened under heating. The partially hardened adhesive layer is in a state called the so-called B-stage. In addition, the thickness of the adhesive layer is not particularly limited, but it is preferably about 0.5 μm to 30 μm. In addition, a copper foil may be further bonded to the adhesive surface of the resin-coated copper foil to obtain a resin-coated copper foil that is a double-sided copper foil.

[Copper-clad laminated board] The present disclosure provides a copper-clad laminated board comprising the above-mentioned copper foil with resin and copper foil or insulating sheet. Copper Clad Laminate is also called CCL (Copper Clad Laminate). Specifically, the copper-clad laminate is a material obtained by pressing the above-mentioned resin-attached copper foil to at least one side or both sides of various known copper foils or insulating sheets under heating. In the case of bonding to one side, a material different from the above-mentioned resin-attached copper foil can be crimped on the other side. In addition, the number of resin-coated copper foils and insulating sheets in the copper-clad laminated board is not particularly limited.

In one of the embodiments, the insulating sheet is preferably a prepreg. Prepreg refers to a sheet material obtained by impregnating a reinforcing material such as glass cloth with resin and hardening it to the B stage (Japanese Industrial Standards (JIS) C 5603). As the resin, insulating resins such as polyimide resin, phenol resin, epoxy resin, polyester resin, liquid crystal polymer, and aromatic polyimide resin can be used. The thickness of the prepreg is not particularly limited, but is preferably about 20 μm to 500 μm. In addition, heating and pressure bonding conditions are not particularly limited, and are preferably about 150°C to 280°C (more preferably about 170°C to 240°C), and preferably about 0.5MPa to 20MPa (more preferably about 1MPa to 8MPa) ).

[Printed Wiring Board] The present disclosure provides a printed wiring board having a circuit pattern on the copper foil surface of the above-mentioned copper clad laminate. The patterning means for forming a circuit pattern on the copper foil surface of a copper-clad laminate can be exemplified by a subtractive method and a semi-additive method. The semi-additive method can be exemplified by the following method: after patterning with a resist film on the copper foil surface of a copper-clad laminate, electrolytic copper plating is performed, the resist is removed, and etching is performed with an alkaline solution. In addition, the thickness of the circuit pattern layer in the printed wiring board is not particularly limited. In addition, it is also possible to obtain a multilayer substrate by using the printed wiring board as a core base material and laminating the same printed wiring board or other known printed wiring boards or build-up printed wiring boards thereon. At the time of lamination, the above-mentioned adhesive and other known adhesives other than the above-mentioned adhesive may be used in combination. In addition, the number of layers in the multilayer substrate is not particularly limited. In addition, each time the layer is stacked, through holes can be inserted and the inside can be plated. The line width/line pitch ratio of the aforementioned circuit pattern is not particularly limited, but is preferably about 1 μm/1 μm to 100 μm/100 μm. In addition, the height of the aforementioned circuit pattern is not particularly limited, but it is preferably about 1 μm to 50 μm.

[Multilayer circuit board] The present disclosure provides a multilayer circuit board, which includes a printed circuit board (1) or a printed circuit board (1), the above-mentioned adhesive layer, and a printed circuit board (2) or a printed circuit board (2). The above-mentioned printed wiring boards (1) to (2) may be the above-mentioned printed wiring boards, and in addition, various well-known printed wiring boards may be used. Similarly, the printed circuit boards (1) to (2) may be the above-mentioned printed circuit boards, and in addition, various well-known printed circuit boards may be used. In addition, the printed wiring board (1) and the printed wiring board (2) may be the same or different. Similarly, the printed circuit board (1) and the printed circuit board (2) may be the same or different.

[Manufacturing method of multilayer circuit board] The present disclosure provides a manufacturing method of multilayer circuit board, which includes the following steps 1 and 2: The step of contacting at least one side of the board (1) or the printed circuit board (1) to produce a substrate with an adhesive layer; Step 2 is to laminate a printed circuit board (2) on the substrate with an adhesive layer Or a printed circuit board (2), and the step of crimping under heating and pressure.

The above-mentioned printed wiring boards (1) to (2) may be the above-mentioned printed wiring boards, and in addition, various well-known printed wiring boards may be used. Similarly, the printed circuit boards (1) to (2) may be the above-mentioned printed circuit boards, and in addition, various well-known printed circuit boards may be used.

In step 1, the means for bringing the above-mentioned adhesive or film-like adhesive material into contact with the adherend is not particularly limited, and examples include various well-known coating means, curtain coaters, roll coaters, and laminators. , Pressing machine, etc.

The heating temperature and pressure bonding time in step 2 are not particularly limited, but it is preferable to heat to 70°C to 200°C after contacting the adhesive or film-like adhesive material of the present invention with at least one surface of the core substrate It takes about 1 minute to 10 minutes for the curing reaction to proceed, and then (ii) to advance the curing reaction of the crosslinking agent, further heat treatment is performed at about 150°C to 250°C for about 10 minutes to 3 hours. In addition, the pressure is not particularly limited, but in the entire period of steps (i) and (ii), it is preferably about 0.5 MPa to 20 MPa, and more preferably about 1 MPa to 8 MPa. [Example]

Hereinafter, the present invention will be specifically explained through examples and comparative examples. However, the description in the above-mentioned preferred embodiment and the following examples are provided for illustrative purposes only, and are not provided for the purpose of limiting the present invention. Therefore, the scope of the present invention is not limited to the embodiments and examples specifically described in this specification, but is only limited to the scope of the patent application. In addition, in each example and comparative example, unless otherwise stated, the numerical values of parts, %, etc. are based on mass.

<Production of polyimide> (Production Example 1) Put 9,9'-bis[4-(3,4-dicarboxyphenoxy) into a reaction vessel equipped with a stirrer, a water trap, a thermometer, and a nitrogen inlet pipe ) Phenyl] pentanoic acid dianhydride (trade name "BPF-PA", manufactured by JFE Chemical Co., Ltd.. Hereinafter referred to as BPF-PA) 290.00 g, cyclohexanone 980.20 g, and methylcyclohexane 196.04 g, and heated Up to 60°C. Next, after dropping 236.60 g of a commercially available dimer diamine (trade name "PRIAMINE 1075", manufactured by Croda Japan Co., Ltd.), the imidization reaction was carried out at 140° C. for 12 hours to obtain polyamide. Amine (1-1) solution (non-volatile content is 31.6%). In addition, the molar ratio of the acid component/amine component of this polyimide was 1.03.

The production examples and comparative production examples other than Production Example 1 were performed in the same manner as in Production Example 1 except that the composition of the resin solution was changed as described in Table 1 to obtain polyimide.

[Table 1]

BPAF: 9,9'-bis(3,4-dicarboxyphenoxy) dianhydride (trade name "BPAF", manufactured by JFE Chemical Co., Ltd.) BAFL: 9,9'-bis(aminophenyl) ) Fu (trade name "BAFL", manufactured by JFE Chemical Co., Ltd.) BisDA-1000: 4,4'-[propane-2,2-diylbis(1,4-phenyleneoxy)]bis-o-benzene Dicarboxylic dianhydride (trade name "BisDA-1000", manufactured by SABIC Innovative Plastics Japan Contracting Company) 1,3-BAC: 1,3-bis(aminomethyl)cyclohexane (manufactured by Mitsubishi Gas Chemical Co., Ltd.)

(Example 1) 10.00 g of a solution of polyimide resin (1-1) and N,N-diglycidyl-4-glycidoxyaniline as a crosslinking agent (Mitsubishi Chemical Co., Ltd. Produced, brand name "jER630") 0.35 g, and 1.35 g of toluene as an organic solvent were mixed, and fully stirred to obtain an adhesive with a non-volatile content of 30.0%.

Except that the composition of the adhesive was changed as described in Table 2, the Examples and Comparative Examples other than Example 1 were performed in the same manner as in Example 1 to obtain an adhesive.

[Table 2]

In addition, organic solvents used in the production of polyimide may also be included in the organic solvent.

<Preparation of Adhesive Sheet> The obtained adhesive was applied to a polyimide film (trade name "Kapton 50EN", manufactured by Toray DuPont Co., Ltd.) by a gap coater so that the thickness after drying was 20 μm ; Film thickness: 12.5 μm; Coefficient of thermal expansion: 15 ppm/°C), then dried at 180°C for 3 minutes to obtain an adhesive sheet.

<Production of copper-clad laminated board> The resin-coated copper foil is produced by superimposing the adhesive surface of the obtained adhesive sheet on a commercially available electrolytic copper foil (trade name "F2-WS", Made by Furukawa Copper Foil Co., Ltd., 18μm thick).

Next, the obtained copper foil with resin was placed on the support for pressing, and the support obtained from the same raw material was interposed from above, and heated and pressed under the conditions of a pressure of 5 MPa, 200° C. and 60 minutes. This produces copper clad laminates.

<Adhesiveness Test> The obtained copper-clad laminated board was measured for peel strength (N/cm) in accordance with JIS C 6481 (test method for copper-clad laminated boards for flexible printed wiring boards). The results are shown in the table.

<Measurement of permittivity and dielectric loss tangent> Approximately 7g of the adhesives of the examples and comparative examples were injected into a fluororesin PFA plate (75mm in diameter, manufactured by Mutual Rika Glass Manufacturing Co., Ltd.), and heated at 30℃× It is cured under the conditions of 10 hours, 70°C×10 hours, 100°C×6 hours, 120°C×6 hours, 150°C×6 hours, and 180°C×12 hours to obtain a dielectric constant of about 300μm. Samples of resin and hardened material for measurement.

Next, for the obtained dielectric constant measurement resin and cured product samples, the dielectric constant at 10 GHz was measured using a commercially available dielectric constant measuring device (cavity resonator type, manufactured by AET) in accordance with JIS C2565 And the dielectric loss tangent. The results are shown in the table.

[table 3]

without

without

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Claims (13)

A polyimide is a reactant of a monomer group containing an aromatic tetracarboxylic anhydride and a diamine, and contains the following extension group in the polymer main chain. The diamine contains a dimer diamine,

100 mol% of the aforementioned diamine contains 40 mol% or less of the diamine containing a stilbene skeleton, and the aforementioned diamine contains 0 to 5% by mass of the diamine-based polymer relative to 100% by mass of the monomer group. Siloxane. The polyimide according to claim 1, wherein the diamine includes the following diamine containing a sulfonium skeleton,

In the above formula, ^{any one of R 1} and R ² represents a group having an amino group, the other represents a hydrogen atom, a hydroxyl group, an alkyl group, or a halogen atom, ^{and any one of R 3} and R ⁴ represents a group having an amino group Group, the other represents a hydrogen atom, a hydroxyl group, an alkyl group or a halogen atom. The polyimide according to claim 1 or 2, wherein the molar ratio of the aromatic tetracarboxylic anhydride to the diamine, that is, the aromatic tetracarboxylic anhydride/diamine is 1.0 to 1.5. An adhesive comprising the polyimide described in any one of claims 1 to 3, a crosslinking agent, and an organic solvent. The adhesive according to claim 4, wherein the polyimide contains 5 to 900 parts by mass of the crosslinking agent and 150 to 900 parts by mass of the polyimide in terms of solid content. Organic solvents. A film-shaped adhesive material comprising a heat-cured product of the adhesive according to claim 4 or 5. An adhesive layer comprising the adhesive according to claim 5 or 6, or the film-like adhesive material according to claim 6. An adhesive sheet comprising the adhesive layer described in claim 7 and a supporting film. A resin-attached copper foil comprising the adhesive layer described in claim 7 and copper foil. A copper clad laminate comprising the resin-attached copper foil of claim 9 and the copper foil or insulating sheet. A printed circuit board having a circuit pattern on the copper foil surface of the copper-clad laminated board according to claim 10. A multilayer circuit board comprising: a printed circuit board (1) or a printed circuit board (1), an adhesive layer according to claim 7, and a printed circuit board (2) or a printed circuit board (2). A manufacturing method of a multilayer circuit board, which includes the following Step 1 and Step 2: Step 1, by combining the adhesive described in claim 4 or 5, or the film-like adhesive material described in claim 6, with the printed circuit board (1) or printed circuit board (1) At least one side contact to make a substrate with an adhesive layer; Step 2 is to laminate a printed circuit board (2) or a printed circuit board (2) on the substrate with an adhesive layer, and heat it And the step of crimping under pressure.