TWI780992B - Polyimide, adhesive, film-like adhesive material, adhesive layer, adhesive sheet, copper foil with resin, copper-clad laminate, printed wiring board, and multilayer wiring board, and method for producing the same - 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-coated copper foil, a copper-clad laminate, 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 comprising an aromatic tetracarboxylic anhydride and a diamine, and contains a terpene group in the polymer main chain, and the diamine comprises Dipolymer diamine; an adhesive comprising polyimide, a crosslinking agent, and an organic solvent; and, a film-like adhesive material, adhesive layer, adhesive sheet, copper foil with resin, copper-clad laminate, printing A circuit board, a multilayer circuit board and a manufacturing method thereof.

Description

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

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

Various known adhesives have been used for manufacturing mobile communication devices such as mobile phones and smart phones or their base station devices, network-related electronic devices such as servers/routers, printed circuit boards included in large computers, and the like.

The present applicant proposes "a polyimide-based adhesive composition, which includes a polyimide resin, a thermosetting resin, a flame retardant, and an organic solvent. The polyimide resin is made of aromatic tetracarboxylic acids and contains More than 30 mol% of specific dimer diamines reacted with diamines" (refer to Patent Document 1). [Prior Art Literature] (patent documents)

Patent Document 1: Japanese Patent No. 5534378

[Problem to be solved by the invention] In recent years, in the above-mentioned network-related electronic devices, it is necessary to transmit and process large-capacity information with low loss and high speed, so the electrical signals processed by the printed circuit boards of these products are also developing at high frequencies. High-frequency electrical signals are prone to attenuation, so it is necessary to further reduce the transmission loss in the printed circuit board. Therefore, low dielectric constant and low dielectric loss tangent (also referred to as low dielectric characteristics) are required for adhesives generally used in printed wiring boards.

However, in Patent Document 1, no study is made on a low dielectric loss tangent. In addition, in recent years, there has been a problem that adhesives with a low dielectric loss tangent are particularly required as electric signals become more high in frequency. [Technical means to solve the problem]

As a result of earnest research, the present inventors have found that the above-mentioned problems can be solved by using a predetermined 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，R ¹和R ²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，R ³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 comprising an aromatic tetracarboxylic acid anhydride and a diamine, and which comprises a terpene group in a polymer main chain, the diamine comprising dimer diamine,

. (Item 2) The polyimide according to the above item, wherein the diamine includes the following diamine having a terpene skeleton,

In the above ^formula , any ^one of R1 and R2 represents a group with an amino group, the other represents a hydrogen atom, a hydroxyl group, an alkyl group or a halogen atom, and any one of ^R3 and R4 represents a group with an amino group , and 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 contains diaminopolysiloxane. (Item 4) The polyimide according to any one of the above items, wherein the molar ratio [aromatic tetracarboxylic anhydride/diamine] of the aromatic tetracarboxylic anhydride to the diamine is 1.0 to 1.5. (Item 5) An adhesive comprising the polyimide according to 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 epoxy, benzoxazine, bismaleimide, and cyanate . (Item 7) The adhesive according to the above item, wherein the epoxy is an epoxy having the following structure,

In the above formula, Y represents a phenylene group or a cyclohexylene group. (Item 8) The adhesive according to any one of the above items, wherein 5 to 900 parts by mass of the crosslinking agent are contained with respect to 100 parts by mass of the polyimide in terms of solid content, and 150 to 900 parts by mass of the aforementioned organic solvent. (Item 9) A film-shaped adhesive material comprising a heat-cured product of the adhesive described in 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 support film. (Item 12) A resin-coated copper foil comprising the adhesive layer described in the above item, and copper foil. (Item 13) A copper-clad laminate comprising the resin-coated copper foil described in the above item, and the copper foil. (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 wiring board comprising: a printed wiring board (1) or a printed circuit board (1), the adhesive layer described in the above item, and a printed wiring board (2) or a printed wiring board (2). (Item 17) A method of manufacturing a multilayer circuit board, which includes the following steps 1 and 2: Step 1, by making the adhesive described in any one of the above items, or the film-like adhesive described in the above items The material is in contact with the printed circuit board (1) or at least one side of the printed circuit board (1) to manufacture a substrate with an adhesive layer; step 2 is to laminate and print on the substrate with an adhesive layer The circuit board (2) or the printed circuit board (2), and the step of crimping under heat and pressure.

In the present disclosure, one or more of the above-mentioned features may be provided in further combinations other than the explicit combinations. [Efficacy of the invention]

By using the polyimide of the present invention, an adhesive with a 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 circuit boards.

Throughout the specification of the present disclosure, the range of numerical values such as each physical property value and content can be appropriately set (for example, selected from upper limit and lower limit values described in each item described below). Specifically, regarding the value α, when the upper limit of the value α can be exemplified by A1, A2, A3, etc., and the lower limit of the value α can be exemplified by B1, B2, B3, etc., the range of the value α can be exemplified below A1, A2, etc. 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. .

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

.

In the present disclosure, "the fenylene group is contained in the polymer main chain" means that the fenylene group is contained in the longest chain constituting the polymer.

＜Aromatic Tetracarboxylic Anhydride＞ Aromatic tetracarboxylic anhydrides can be used alone or in combination of two or more. Aromatic tetracarboxylic anhydrides include tetracarboxylic anhydrides having a fennel skeleton, symmetrical aromatic tetracarboxylic anhydrides, and the like.

上述式中，R ¹和R ²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，R ³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R ¹和R ²及/或R ³和R ⁴一起形成酸酐基的基團。 (Tetracarboxylic anhydride containing a fennel skeleton) In one embodiment, the tetracarboxylic anhydride containing a fennel skeleton is represented by the following general formula,

In the above ^formula , any ^one of R1 and R2 represents a group with an acid anhydride group, the other represents a hydrogen atom, a hydroxyl group, an alkyl group or a halogen atom, and any one of ^R3 and R4 represents a group with an acid anhydride group , and 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.

As a group having an acid anhydride group, 3,4-dicarboxyphenoxy, 3,4-dicarboxyphenyl, etc. can be illustrated.

When R ¹ and R ² and/or R ³ and R ⁴ together form an acid anhydride group, the formed acid anhydride group may, for example, be 3,4-dicarboxyphenyl or the like.

As an alkyl group, a linear alkyl group, a branched alkyl group, a cycloalkyl group, etc. can be illustrated.

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, further preferably about 1-16, particularly preferably about 1-12.

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

Branched alkyl groups include isopropyl, isobutyl, isopentyl, isohexyl, isodecyl and the like.

As a cycloalkyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group etc. can be illustrated. In addition, one or more hydrogen atoms on each ring of the cycloalkyl group may be substituted with a straight-chain alkyl group (groups exemplified above, etc.) or a branched alkyl group (groups exemplified above, etc.).

As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. can be illustrated.

Tetracarboxylic acid anhydrides containing a fennel skeleton can be exemplified: 9,9'-bis[4-(3,4-dicarboxyphenoxy)phenyl] fennelic dianhydride, 9,9'-bis(3,4- Dicarboxyphenoxy) stilnic acid dianhydride, etc.

The upper limit of the content of the tetracarboxylic anhydride containing the terpene skeleton in 100 mol% of the 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 fennel 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 acid anhydride containing the fennel 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% by mass % 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 fennel skeleton-containing tetracarboxylic anhydride 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 anhydride containing the fennel 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 anhydride containing a terpene skeleton in 100 mol% of the monomer group is preferably about 0 to 75 mol%.

The upper limit of the content of the tetracarboxylic anhydride containing the fennel 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, 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 Wait. In one embodiment, the content of the tetracarboxylic acid anhydride having a 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、-SO ₂-、-CO-、-O-、-O-C ₆H ₄-C(CH ₃) ₂-C ₆H ₄-O-、-COO-(CH ₂) _p-OCO-或-COO-H ₂C-HC(-O-C(=O)-CH ₃)-CH ₂-OCO-，p表示1～20的整數。 (Symmetric Aromatic Tetracarboxylic Anhydride) In the present disclosure, "symmetric aromatic tetracarboxylic anhydride" means an aromatic tetracarboxylic anhydride having a symmetry axis (for example, C2 symmetry axis) in the molecule. Symmetrical aromatic tetracarboxylic anhydrides can be exemplified: Symmetrical aromatic tetracarboxylic anhydrides 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-, 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'-diphenyltetracarboxylic 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)pyridine dianhydride, 2, 2',3,3'-Biphenyltetracarboxylic dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, pyromellitic dianhydride, 1,2,3,4- Benzene tetracarboxylic anhydride, 1,4,5,8-naphthalene tetracarboxylic anhydride, 2,3,6,7-naphthalene tetracarboxylic anhydride, etc.

Among the above-mentioned symmetrical aromatic tetracarboxylic anhydrides, from the viewpoints of compatibility between aromatic tetracarboxylic anhydrides and diamines, adhesion at room temperature, and heat-resistant adhesion, it is preferred to be selected from the group consisting of 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 the symmetrical aromatic tetracarboxylic anhydride in 100 mol% of the 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 symmetrical aromatic tetracarboxylic anhydride in 100 mol % of the aromatic tetracarboxylic anhydride is preferably about 50 to 100 mol %.

The upper limit of content of the symmetrical aromatic tetracarboxylic anhydride in 100 mass % of aromatic tetracarboxylic anhydrides can be illustrated: 100 mass %, 90 mass %, 80 mass %, 70 mass %, 60 mass %, 55 mass %, 50 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 to 100% by mass, more preferably about 50 to 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 mol % 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 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 contain aromatic tetracarboxylic anhydrides (also referred to as other aromatic tetracarboxylic anhydrides) that are neither the above-mentioned fennel skeleton-containing tetracarboxylic anhydrides nor symmetrical 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% 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, around 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%, about 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, approximately 0% by mass, etc.

The upper limit of the content of the 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%, and the like. In one embodiment, the content of the aromatic tetracarboxylic acid anhydride in 100 mol% of the monomer group is preferably about 50-75 mol%.

The upper limit of the aromatic tetracarboxylic anhydride content 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＞ Diamines can be used alone or in combination of two or more. Examples of diamine include dimer diamine, diamine having a stilbene skeleton, diaminopolysiloxane, and the like.

(Dipolymer Diamine) In the present invention, dimer diamine refers to a dimer of unsaturated fatty acids such as oleic acid, that is, a substance obtained by substituting all carboxyl groups of dimer acid with primary amine groups (see Japan JP-A-9-12712, etc.), various known dimer diamines can be used without particular limitation. The non-limiting general formulas of dimer diamines are shown below (in each formula, m+n=6-17 is preferable, p+q=8-19 is preferable, and the dotted line represents a carbon-carbon single bond or carbon-carbon double bonds).

Examples of commercially available dimer diamines include: Versamine 551 (manufactured by Japan Koning Co., Ltd.), Versamine 552 (manufactured by Japan Koning Co., Ltd.; hydrogenated product of Versamine 551), PRIAMINE 1075, and PRIAMINE 1074 (both from Japan Made by Koluoda Co., Ltd.), etc.

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

The upper limit of the dimer diamine content 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 to 50% by mass.

式中，R ¹和R ²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，R ³和R ⁴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 fennel skeleton) In one embodiment, the diamine containing a fennel skeleton is represented by the following general formula,

^In the ^formula , any ^one of R1 and R2 represents a group with an amino group, the other represents a hydrogen atom, a hydroxyl group, an alkyl group or a halogen atom, and any one of ^R3 and R4 represents a group with an amino group , and 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 an amino group and a group in which at least one hydrogen atom in a functional group is substituted with an amino group. The group having an amino group includes, for example, an amino group, an alkylamino group, an arylamine group, an alkoxyamine group, an aryloxyamine group, and the like.

As an aryl group, a monocyclic aryl group, a condensed ring aryl group, etc. can be illustrated. In addition, one or more hydrogen atoms of the aryl group may be substituted with 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.

Diamines containing a stilbene skeleton can be exemplified: 9,9'-bis(aminophenyl)stilbene, 9,9'-bis(4-amino-3-methylphenyl)stilbene, 9,9'- Bis(4-amino-3-fluorophenyl) fluorene, 9,9'-bis(4-amino-3-hydroxyphenyl) fluorine, 9,9'-bis(4-methyl-3-amine phenyl) fluorene, 9,9'-bis(4-fluoro-3-aminophenyl) fluorine, 9,9'-bis(4-hydroxy-3-aminophenyl) fluorine, 9,9' - bis[4-(4-aminophenoxy)phenyl]fenoxene and the like.

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

The upper limit of the content of the diamine component containing a fennel 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 embodiment, from the viewpoint of improving dielectric properties, the content of the diamine component containing the fennel skeleton in 100 mol% of diamine is preferably about 20 to 80% by mass.

The upper limit of the content of the diamine containing the fennel 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 Mole %, 30 Mole %, 20 Mole %, 10 Mole %, 5 Mole %, 0 Mole %, etc. In one embodiment, the content of the diamine containing the fennel skeleton in 100 mol% of the monomer group is preferably 0-50 mol%.

The upper limit of the content of diamine containing a fennel skeleton 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 can be Examples: 40% by mass, 30% by mass, 20% by mass, 10% by mass, 5% by mass, 0% by mass, and the like. In one embodiment, the content of the diamine having a stilbene skeleton in 100% by mass of the monomer group is preferably 0 to 50% by mass.

The upper limit of the ratio of the amount of diamine containing a stilbene skeleton to the amount of dimer diamine (diamine containing a 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 embodiment, from the viewpoint of improving flexibility, adhesiveness, and dielectric properties, the ratio of the amount of diamine containing a stilbene skeleton to the amount of diamine dimer (diamine containing a stilbene skeleton /dipolymer diamine), preferably about 0.25 to 4.00.

(Diaminopolysiloxane) Diaminopolysiloxane, for example: α,ω-bis(2-aminoethyl)polydimethylsiloxane, α,ω-bis(3-aminopropyl)polydimethylsiloxane Oxane, α,ω-bis(4-aminobutyl)polydimethylsiloxane, α,ω-bis(5-aminopentyl)polydimethylsiloxane, α,ω-bis(aminobutyl)polydimethylsiloxane, [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 diaminopolysiloxane in 100 mol % of diamine can be exemplified: 5 mol %, 4 mol %, 3 mol %, 2 mol %, 1 mol %, etc.; the lower limit Examples include: 4 mol%, 3 mol%, 2 mol%, 1 mol%, 0 mol%, and the like. In one embodiment, the content of diaminopolysiloxane in 100 mol % of diamine is preferably about 0 to 5 mol % from the viewpoint of improving flexibility.

The upper limit of the content of diaminopolysiloxane in 100% by mass of diamine can be exemplified: 5% by 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, the content of diaminopolysiloxane in 100% by mass of diamine is preferably about 0 to 5% by mass from the viewpoint of improving flexibility.

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

(other diamines) In one embodiment, the monomer group may contain diamines (also referred to as other diamines) other than the above. Examples of other diamines include: alicyclic diamine, bisaminophenoxyphenylpropane, diaminodiphenyl ether, phenylenediamine, diaminodiphenylsulfide, diaminodiphenyl Diaminobenzophenone, diaminodiphenylmethane, diaminophenylpropane, diaminophenylhexafluoropropane, diaminophenylphenylethane, diaminophenoxy Benzene, Bisaminobenzylbenzene, Bisaminodimethylbenzylbenzene, Bisaminobistrifluoromethylbenzylbenzene, Aminophenoxybiphenyl, Aminophenoxyphenyl Ketone, aminophenoxyphenylsulfide, aminophenoxyphenylsulfide, aminophenoxyphenylether, aminophenoxyphenylpropane, bis(aminophenoxybenzoyl ) benzene, bis(aminophenoxy-α,α-dimethylbenzyl)benzene, bis[(aminoaryloxy)benzoyl]diphenyl ether, bis(amino-α ,α-Dimethylbenzylphenoxy)benzophenone, bis[amino-α,α-dimethylbenzylphenoxy]diphenylphenone, 4,4'-bis[amine phenoxyphenoxy]diphenylphenone, diaminodiaryloxybenzophenone, diaminoaryloxybenzophenone, 6,6'-bis(aminoaryloxy base)-3,3,3',3'-tetramethyl-1,1'-spirobisindan, bis(aminoalkyl)ether, bis(aminoalkoxyalkyl)ether, bis( Aminoalkoxy)alkane, bis[(aminoalkoxy)alkoxy]alkane, (poly)ethylene glycol bis(aminoalkyl)ether, bis(aminoaryloxy)pyridine, Alkyl diamine, etc.

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, for example: 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy base) phenyl] propane, etc.

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

As phenylenediamine, phenylenediamines, such as p-phenylenediamine and m-phenylenediamine, etc. can be illustrated.

Diaminodiphenylsulfide, for example: 3,3'-diaminodiphenylsulfide, 3,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfide base sulfide etc.

Diaminodiphenylene, for example: 3,3'-diaminodiphenylene, 3,4'-diaminodiphenylene, 4,4'-diaminodiphenylene, etc. .

Diaminobenzophenone, for example: 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, etc. .

Diaminodiphenylmethane, for example: 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, etc. .

Diaminophenylpropane, for example: 2,2-bis(3-aminophenyl)propane, 2,2-bis(4-aminophenyl)propane, 2-(3-aminophenyl) -2-(4-aminophenyl)propane, etc.

Diaminophenylhexafluoropropane, for example: 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.

Diaminophenylphenylethane, for example: 1,1-bis(3-aminophenyl)-1-phenylethane, 1,1-bis(4-aminophenyl)-1- Phenylethane, 1-(3-aminophenyl)-1-(4-aminophenyl)-1-phenylethane and the like.

Bisaminophenoxybenzene, for example: 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(3 -aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene and the like.

Bisaminobenzoylbenzene can be exemplified: 1,3-bis(3-aminobenzoyl)benzene, 1,3-bis(4-aminobenzoyl)benzene, 1,4- Bis(3-aminobenzoyl)benzene, 1,4-bis(4-aminobenzoyl)benzene, etc.

Bisaminodimethylbenzylbenzene, for example: 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.

Bisaminobistrifluoromethylbenzylbenzene, for example: 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, etc.

Aminophenoxybiphenyl, for example: 2,6-bis(3-aminophenoxy)benzonitrile, 4,4'-bis(3-aminophenoxy)biphenyl, 4,4 '-bis(4-aminophenoxy)biphenyl, etc.

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

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

Aminophenoxyphenylpropane, for example: 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, etc.

Bis(aminophenoxybenzoyl)benzene can be exemplified: 1,3-bis[4-(3-aminophenoxy)benzoyl]benzene, 1,3-bis[4-( 4-aminophenoxy)benzoyl]benzene, 1,4-bis[4-(3-aminophenoxy)benzoyl]benzene, 1,4-bis[4-(4- Aminophenoxy) benzoyl] benzene, etc.

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-aminophenoxy) oxy)-α,α-dimethylbenzyl]benzene, 1,4-bis[4-(4-aminophenoxy)-α,α-dimethylbenzyl]benzene, etc.

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

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

Bis[amino-α,α-dimethylbenzylphenoxy]diphenylphenoxide, for example: 4,4'-bis[4-(4-amino-α,α-dimethylbenzene Methyl)phenoxy]diphenylsulfone etc.

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

Diaminodiaryloxybenzophenone, for example: 3,3'-diamino-4,4'-diphenoxybenzophenone, 3,3'-diamino-4, 4'-Diphenoxybenzophenone, etc.

Diaminoaryloxybenzophenone, for example: 3,3'-diamino-4-phenoxybenzophenone, 3,3'-diamino-4-biphenyloxydiphenone Benzophenone etc.

6,6'-bis(aminoaryloxy)-3,3,3',3'-tetramethyl-1,1'-spirobisindan can be exemplified by: 6,6'-bis(3 -aminophenoxy)-3,3,3',3'-tetramethyl-1,1'-spirobisindane, 6,6'-bis(4-aminophenoxy)-3, 3,3',3'-tetramethyl-1,1'-spirobisindane, etc.

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

Bis(aminoalkoxyalkyl) ethers can be exemplified: bis[2-(aminomethoxy)ethyl]ether, bis[2-(2-aminoethoxy)ethyl]ether, bis[2-(aminoethoxy)ethyl]ether, [2-(3-Aminopropoxy)ethyl]ether, etc.

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

Bis[(aminoalkoxy)alkoxy]alkane, for example: 1,2-bis[2-(aminomethoxy)ethoxy]ethane, 1,2-bis[2-(2 -aminoethoxy)ethoxy]ethane and the like.

(Poly)ethylene glycol bis(aminoalkyl)ether, for example: ethylene glycol bis(3-aminopropyl)ether, diethylene glycol bis(3-aminopropyl)ether, triethylene glycol Alcohol bis(3-aminopropyl) ether, etc.

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

Alkylene diamines, for example: ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane alkanes, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminodecane One alkane, 1,12-diaminododecane, etc.

In one embodiment, 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%, 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 embodiment, 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 embodiment, 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, around 0% by mass, etc.

The upper limit of the diamine content 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 embodiment, the content of the 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 by: 45% by mass, 40% by mass %, 35% by mass, 30% by mass, 25% by mass, etc. In one embodiment, the content of the diamine in 100% by mass of the monomer group is preferably about 25 to 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 [aromatic tetracarboxylic anhydride/diamine] of aromatic tetracarboxylic anhydride to 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 [aromatic tetracarboxylic anhydride/diamine] of the aromatic tetracarboxylic anhydride to the diamine is preferably 0.5 to 1.5.

＜Other monomers＞ In one embodiment, the monomer group may contain monomers (also referred to as other monomers) that are neither aromatic tetracarboxylic acid anhydrides nor diamines. As other monomers, aliphatic tetracarboxylic anhydrides and the like can be illustrated.

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, around 0% by mass, etc.

＜Physical properties of polyimide, etc.＞ The upper limit of the weight average molecular weight of the above-mentioned polyimide can be exemplified: 50000, 40000, 30000, 20000, 10000, 7500, 5500, 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 above-mentioned polyimide can be exemplified: 40000, 30000, 20000, 10000, 7500, 5000, 3000, etc.; . In one embodiment, the polyimide has a number average molecular weight of 2,000 to 40,000 from the viewpoint of dielectric properties, solvent solubility, and flexibility.

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

The upper limit of the softening point of the above 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°C, etc. ℃, 25℃, 20℃, etc. In one embodiment, the softening point of the polyimide is preferably 20 to 220° C. from the viewpoint of workability, heat resistance, and solvent solubility.

The softening point can be obtained using a commercially available measuring device (“ARES-2KSTD-FCO-STD” manufactured by Rheometric Scientific Co., Ltd.) or the like.

<Manufacturing method of polyimide, etc.> The above polyimide can be produced by various known methods. The production method of polyimide can be exemplified: a method comprising the following steps: making a monomer group including aromatic tetracarboxylic anhydride and diamine including dimer diamine, etc., preferably at 60 to 120 °C, more preferably at a temperature of about 80-100 °C to carry out polyaddition reaction, preferably about 0.1-2 hours, more preferably about 0.1-0.5 hours, to obtain poly-adducts; make the obtained poly-addition The finished product is preferably carried out at a temperature of about 80-250°C, more preferably about 100-200°C, for an imidization reaction, that is, a dehydration ring-closure reaction, preferably about 0.5-50 hours, more preferably 1-200 hours. 20 hours or so.

In addition, in the step of carrying out 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 below can be used alone or in combination of two or more. 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; and the like. In addition, examples of the dehydrating agent include aliphatic acid anhydrides such as acetic anhydride, aromatic acid anhydrides such as benzoic anhydride, and the like.

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

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

The upper limit of the polyimide content in 100% by mass of the above-mentioned 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% by mass, % by 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 the crosslinking agent, various known crosslinking agents can be used without particular limitation as long as they can function as a polyimide crosslinking agent. The crosslinking agent can be used alone or in combination of two or more. The crosslinking agent is preferably at least one selected from the group consisting of epoxy, benzoxazine, bismaleimide and cyanate.

(epoxide) Epoxides can be exemplified: phenol novolak type epoxy, cresol novolak type epoxy, bisphenol A type epoxy, bisphenol F type epoxy, bisphenol S type epoxy, hydrogenated bisphenol Phenol A-type epoxide, hydrogenated bisphenol F-type epoxide, stilbene-type epoxide, triazine-skeleton-containing epoxide, fennel-skeleton-containing epoxide, linear aliphatic epoxide , alicyclic epoxides, glycidylamine epoxides, trisphenolic methane epoxides, alkyl modified trisphenolic methane epoxides, biphenyl epoxides, containing dicyclopentyl Epoxides with diene skeletons, epoxides with naphthalene skeletons, aryl alkene type epoxides, tetraglycidyl xylyl diamine, dimer acid modified products of the above epoxides Polymer acid modified epoxy, dimer acid diglycidyl ester, etc. In addition, examples of commercially available epoxy oxides include "jER828", "jER834" and "jER807" manufactured by Mitsubishi Chemical Co., Ltd.; "ST-3000" manufactured by Nippon Steel Chemical Co., Ltd.; Daicel Chemical Co., Ltd. "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-resistant adhesiveness, moisture-absorbing solder heat resistance, and low dielectric properties, preferred are bisphenol A-type epoxy oxides, bisphenol F-type epoxy oxides, and hydrogenated bisphenol A-type epoxy oxides. 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, tetraglycidyldiamine having the following structure has good compatibility with the aforementioned polyimide. In addition, when this component is used, the adhesive layer becomes easy to have a low-loss elastic modulus, and its heat-resistant adhesive properties and low dielectric properties also become favorable.

In the above formula, Y represents a phenylene group or a cyclohexylene group.

When using an epoxy as a crosslinking agent, various well-known hardening|curing agents for epoxy can be used together. Hardeners for epoxy can be used alone or in combination of two or more. Examples of curing agents for epoxides include: succinic anhydride, phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride Diformic anhydride, 4-methylhexahydrophthalic anhydride, or a mixture of 4-methylhexahydrophthalic anhydride and hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride Hydrophthalic anhydride, nadic anhydride, methylnadic anhydride, norbornane-2,3-dicarboxylic anhydride, methylnorbornane-2,3-dicarboxylic anhydride, methylcyclo Anhydride hardeners such as hexene dicarboxylic anhydride, 3-dodecenyl succinic anhydride, and octenyl succinic anhydride; dicyandiamide (DICY), aromatic diamine (trade names "LonzacureM-DEA", "LonzacureM-DETDA ", etc., are manufactured by Lonza Japan Co., Ltd.), amine-based hardeners such as aliphatic amines; Phenolic hardeners such as phosphazene containing phenolic hydroxyl group (trade name "SPH-100" manufactured by Otsuka Chemical Co., Ltd., etc.), cyclic phosphazene compounds, maleic acid-modified rosin or its hydrogenated product, etc. Rosin-based crosslinking agent, etc. Among them, a phenolic curing agent is preferred, and a phosphazene-based curing agent containing a phenolic hydroxyl group is particularly preferred. The amount of the curing agent used is not particularly limited, but is preferably about 0.1 to 120% by mass, more preferably about 10 to 40% by mass, when the solid content of the adhesive is 100% by mass.

In the case of using an epoxy and a curing agent for epoxy in combination as a crosslinking agent, a reaction catalyst may further be used in combination. The reaction catalyst can be used alone or in combination of two or more. The reaction catalyst can be exemplified: 1,8-diaza-bicyclo[5.4.0]undecene-7, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, Tertiary amines such as (dimethylaminomethyl)phenol; 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole and other imidazoles ; Tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, phenylphosphine and other organic phosphines; tetraphenylphosphonium tetraphenyl borate, 2-ethyl-4-methyl Tetraphenylboron salts such as imidazole tetraphenyl borate, N-methylmorpholine tetraphenyl borate, and the like. In addition, the usage-amount of this reaction catalyst is not specifically limited, When the solid content of the said adhesive is made into 100 mass %, it is preferable that it is about 0.01-5 mass %.

(benzoxazine) Benzoxazine can be exemplified: 6,6-(1-methylethylene)bis(3,4-dihydro-3-phenyl-2H-1,3-benzoxazine), 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 or the like may be bonded to the nitrogen of the oxazine ring. In addition, commercially available products of benzoxazine include "benzoxazine F-a type" or "benzoxazine P-d type" manufactured by Shikoku Chemical Industry Co., Ltd., and "RLV-100 type" manufactured by Air Water Co., Ltd. "Wait.

(bismaleimide) Examples of bismaleimide include: 4,4'-diphenylmethane bismaleimide, m-phenylene bismaleimide, bisphenol A diphenyl ether bismaleimide , 3,3'-Dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide Amide, 1,6'-bismaleimide-(2,2,4-trimethyl)hexane, 4,4'-diphenyl ether bismaleimide, 4,4' -Diphenyl bismaleimide, etc. In addition, as a commercial item of bismaleimide, "BAF-BMI" by JFE Chemical Co., Ltd., etc. can be illustrated.

(cyanate) Cyanate, for example: 2-allylphenol cyanate, 4-methoxyphenol cyanate, 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-paraffin (4-cyanooxyphenyl) Ethane, 4-cumylphenol cyanate, 1,1-bis(4-cyanooxyphenyl)ethane, 4,4'-bisphenol cyanate and 2,2-bis(4- Cyanooxyphenyl) propane, etc. Moreover, "PRIMASET BTP-6020S (made by Lonza Japan Co., Ltd.)" etc. can be illustrated as a commercial item of cyanate ester.

In the above adhesive, the upper limit of the content of the crosslinking agent is exemplified by 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 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 (in terms of solid content) of the polyimide.

The upper limit of the content of the crosslinking agent in 100% by mass of the above adhesive 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＞ As the organic solvent, various known organic solvents can be used alone or in combination of two or more. Examples of organic solvents include: N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, dimethylsulfoxide, 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, etc.

In addition, the content of the organic solvent in the adhesive is not particularly limited, but it is preferably an amount such that the mass of the solid content becomes 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 can be exemplified as follows: 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, 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 portion etc. 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 (in terms of solid content) of the polyimide.

＜Flame retardant＞ In one embodiment, the above-mentioned adhesive contains a flame retardant. Flame retardants can be used alone or in combination of two or more. As a flame retardant, a phosphorus flame retardant, an inorganic filler, etc. can be illustrated.

(Phosphorus Flame Retardant (Phosphorous Flame Retardant)) Examples of phosphorus-based flame retardants include polyphosphoric acid, phosphoric acid esters, phosphazene derivatives not containing phenolic hydroxyl groups, and the like. Among the phosphazene derivatives, cyclic phosphazene derivatives are preferred from the viewpoint of flame retardancy, heat resistance, bleeding resistance, and the like. Commercially available products of 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, examples of the inorganic filler include silica fillers, phosphorus fillers, fluorine fillers, inorganic ion exchanger fillers, and the like. Examples of commercially available products include FB-3SDC manufactured by Denka Co., Ltd., Exolit OP935 manufactured by Clariant Chemicals 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 is exemplified by 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, the content of the flame retardant in the adhesive is preferably 1 to 150 parts by mass relative to 100 parts by mass (in terms of solid content) of the polyimide.

<Reactive Alkoxysilyl Compounds> In one embodiment, the above-mentioned adhesive further contains a compound of the general formula Z-Si(R ¹ ) _a (OR ² ) _3-a (wherein, Z represents an acid anhydride containing Reactive alkoxy group represented by R1 represents hydrogen or a hydrocarbon group with ¹ to 8 carbon atoms, R2 represents a hydrocarbon group with 1 to 8 carbon atoms, and a represents 0, 1 or ² . Silicon-based compounds. By utilizing the reactive alkoxy silicon-based compound, the low dielectric property of the adhesive layer formed by the adhesive of the present invention can be maintained and its melt viscosity can be adjusted. As a result, the bleeding of the hardened layer from the edge of the substrate can be suppressed while enhancing the interfacial adhesion between the adhesive layer and the substrate (so-called anchoring effect).

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

Compounds where Z contains an amino group, for example: N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-amino Propyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane and 3-ureidopropyltrialkoxysilane, etc. As a compound in which Z contains an epoxy group, for example: 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3 -Glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, etc. Examples of compounds in which Z contains a thiol group include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and 3-mercapto Propylmethyldiethoxysilane, etc. Among them, a compound in which Z contains an amine group is preferable from the viewpoint of good reactivity and flow control effect.

In the above-mentioned adhesive, the upper limit of the content of the reactive alkoxysilyl compound is exemplified by 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, the content of the reactive alkoxysilyl compound in the adhesive is preferably 0.01 to 5 parts by mass relative to 100 parts by mass (in terms of solid content) of the polyimide.

The above-mentioned adhesive may contain, as an additive, a substance other than any one of the above-mentioned polyimide, cross-linking agent, organic solvent, flame retardant, and reactive alkoxysilyl compound.

Examples of additives include: ring-opening esterification catalyst, dehydrating agent, plasticizer, weather resistance agent, antioxidant, heat stabilizer, lubricant, antistatic agent, whitening agent, colorant, conductive agent, mold release agent , surface treatment agent, viscosity regulator, silica filler and fluorine filler, etc.

In one embodiment, the content of the additive can be, for example, less than 1 part by mass, less than 0.1 part by mass, less than 0.01 part by mass, or 0 part by mass with respect to 100 parts by mass of the adhesive.

In another embodiment, with respect to 100 parts by mass (in terms of solid content) of the above-mentioned 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, crosslinking agent, and if necessary, a flame retardant, a reactive alkoxysilyl compound, and additives in an organic solvent.

[Film Adhesive Material] The present disclosure provides a film-like adhesive material comprising a heat-hardened product of the above-mentioned adhesive. The method for producing a film-like adhesive material includes, for example, a method comprising the steps of applying the above-mentioned adhesive to a suitable support, volatilizing the organic solvent by heating to harden it, and removing the adhesive from the support. Steps of peeling etc. The thickness of the adhesive material is not particularly limited, but is preferably about 3 μm to 40 μm. As a support body, the following materials etc. can be illustrated.

[adhesive layer] The present disclosure provides an adhesive layer comprising an adhesive or the aforementioned film-like adhesive material. When manufacturing the said adhesive layer, the said adhesive and various well-known adhesives other than the said adhesive can be used together. Similarly, the above-mentioned film-form adhesive material and various well-known film-form adhesive materials other than the above-mentioned film-form adhesive material can also be used together.

[adhesive sheet] The present disclosure provides an adhesive sheet, which includes the above-mentioned adhesive layer and a supporting film.

As the support film, a plastic film can be exemplified. Plastics, for example: polyester, polyimide, polyimide-silicon dioxide hybrid, polyethylene, polypropylene, polyethylene terephthalate, polyethylene naphthalate, polymethyl Methyl acrylate resin, polystyrene resin, polycarbonate resin, acrylonitrile-butadiene-styrene resin, made of ethylene terephthalate, phenol, phthalic acid, hydroxynaphthoic acid, etc. and p-hydroxybenzene Aromatic polyester resins obtained from formic acid (so-called liquid crystal polymers, "Vecstar" manufactured by Kuraray Co., Ltd., etc.), etc.

In addition, when applying the above-mentioned adhesive to the support film, the aforementioned coating means can be employed. The thickness of the coating layer 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 disclosure provides a resin-attached copper foil, which includes the above-mentioned adhesive layer and copper foil. Specifically, the resin-coated copper foil is a material obtained by applying or bonding the adhesive or the film-like adhesive material to 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, and more preferably about 2 μm to 38 μm. In addition, this copper foil may be a copper foil subjected to various surface treatments (roughening, antirust, etc.). Examples of the antirust treatment include plating treatment using a plating solution containing nickel (Ni), zinc (Zn), tin (Sn), and so-called mirror treatment such as chromate treatment. Moreover, as a coating means, the method mentioned above can be illustrated.

In addition, the adhesive layer of the resin-coated copper foil may be an uncured adhesive layer, or may be an adhesive layer that is partially or completely cured by heating. The partially hardened adhesive layer is in what is referred to as the B-stage. In addition, the thickness of the adhesive layer is not particularly limited, but is preferably about 0.5 μm to 30 μm. Moreover, you may make it the resin-coated copper foil of double-sided copper foil by bonding copper foil to the adhesive surface of this resin-coated copper foil further.

[Copper Clad Laminate Board] The present disclosure provides a copper-clad laminate, which includes the resin-attached copper foil and the copper foil or an insulating sheet. Copper Clad Laminate is also called CCL (Copper Clad Laminate). Specifically, the copper-clad laminate is a material obtained by pressing the resin-coated copper foil to at least one 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-coated 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 laminate is not particularly limited.

In one embodiment, the insulating sheet is preferably a prepreg. Prepreg is a sheet-like material obtained by impregnating a reinforcing material such as glass cloth with a resin and curing it to the B stage (Japanese Industrial Standard (JIS) C 5603). As the resin, insulating resins such as polyimide resins, phenol resins, epoxy resins, polyester resins, liquid crystal polymers, and aramid resins 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 crimping conditions are not particularly limited, but 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 Circuit 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. As a patterning means for forming a circuit pattern on the copper foil surface of a copper-clad laminate, a subtractive method and a semi-additive method can be exemplified. As the semi-additive method, a method of patterning the copper foil surface of the copper-clad laminate with a resist film, performing electrolytic copper plating, removing the resist, and etching with an alkaline solution can be exemplified. In addition, the thickness of the circuit pattern layer in this printed wiring board is not specifically limited. In addition, a multilayer substrate can also be obtained by using this printed wiring board as a core base material and laminating the same printed wiring board or other known printed wiring boards or laminated printed wiring boards thereon. For lamination, the above-mentioned adhesives and other known adhesives other than the above-mentioned adhesives may be used in combination. In addition, the number of laminated layers in the multilayer substrate is not particularly limited. In addition, through-holes can be inserted and the inside can be plated every time a layer is built up. The line width/space 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 is preferably about 1 μm to 50 μm.

[Multilayer circuit board] The 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, or may be various known printed wiring boards. Likewise, the printed circuit boards (1) to (2) may be the above-mentioned printed circuit boards, or may be various known printed circuit boards. In addition, the printed wiring board (1) and the printed wiring board (2) may be the same or different. Likewise, the printed circuit board (1) and the printed circuit board (2) can also be the same or different.

[Manufacturing method of multilayer circuit board] The disclosure provides a method for manufacturing a multilayer circuit board, which includes the following steps 1 and 2: Step 1 is a step of manufacturing a base material with an adhesive layer by bringing the above-mentioned adhesive or the above-mentioned film-like adhesive material into contact with the printed circuit board (1) or at least one side of the printed circuit board (1); Step 2 is a step of laminating a printed circuit board (2) or a printed circuit board (2) on the substrate with an adhesive layer, and performing crimping under heating and pressure.

The above-mentioned printed wiring boards (1) to (2) may be the above-mentioned printed wiring boards, or may be various known printed wiring boards. Likewise, the printed circuit boards (1) to (2) may be the above-mentioned printed circuit boards, or may be various known printed circuit boards.

In step 1, the means for bringing the adhesive or film-like adhesive material into contact with the adherend is not particularly limited, and examples include various known coating means, curtain coater, roll coater, and laminator , Compression machines, etc.

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

Hereinafter, the present invention will be specifically described through examples and comparative examples. However, the description in the above-mentioned preferred embodiment and the following examples are provided for the purpose of illustration 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 limited only by the claims. In addition, in each Example and a comparative example, unless otherwise stated, the numerical value of a part, %, etc. is based on mass.

＜Manufacture of polyimide＞ (Manufacturing example 1) Put 9,9'-bis[4-(3,4-dicarboxyphenoxy)phenyl]oxalic acid dianhydride (trade name "BPF -PA", manufactured by JFE Chemical Co., Ltd. (hereinafter abbreviated as BPF-PA), 290.00 g of cyclohexanone 980.20 g, and 196.04 g of methylcyclohexane, and heated to 60°C. Next, 236.60 g of a commercially available dimer diamine (trade name "PRIAMINE 1075", manufactured by Croda Japan Co., Ltd.) was added dropwise, and imidization reaction was carried out at 140°C for 12 hours to obtain polyamide Solution of amine (1-1) (31.6% of non-volatile content). In addition, the molar ratio of the acid component/amine component of this polyimide was 1.03.

In the production examples and comparative production examples other than the production example 1, except that the composition of the resin solution was changed as described in Table 1, polyimide was obtained in the same manner as in the production example 1.

[Table 1] (A) Aromatic tetracarboxylic anhydride (B) Diamine solvent non-volatile components (A)/(B) Resin dielectric constant (10GHz) Resin dielectric loss tangent (10GHz) Weight average molecular weight Production Example 1 (Polyimide (1-1)) BPF-PA 290.00g (b1)PRIAMINE1075 236.60g Cyclohexanone 980.20g Methylcyclohexane 196.04g 31.6% 1.03 2.26 0.00146 34600 Production Example 2 (Polyimide (1-2)) BPAF 250.00g (b1)PRIAMINE1075 285.91g Cyclohexanone 989.00g Methylcyclohexane 197.80g 31.4% 1.03 2.22 0.00131 36500 Production Example 3 (Polyimide (1-3)) BisDA-1000 300.00g (b1) PRIAMINE1075 201.76g (b2) BAFL 61.26g Cyclohexanone 1039.82g Methylcyclohexane 207.96g 31.5% 1.05 2.36 0.00152 35700 Production example 4 (polyimide (1-4)) BisDA-1000 320.00g (b1) PRIAMINE1075 94.95g (b2) BAFL 142.95g Cyclohexanone 955.18g Methylcyclohexane 207.96g 31.5% 1.05 2.46 0.0040 33600 Production example 5 (polyimide (1-5)) BisDA-1000 300.00g (b1) PRIAMINE1075 186.92g (b2) BAFL 61.26g (b3) Diamino polysiloxane (KF-8010) 24.18g Cyclohexanone 1005.04g Methylcyclohexane 201.01g 31.5% 1.05 2.40 0.00170 35500 Production example 6 (polyimide (1-6)) BPAF 250.00g (b1) PRIAMINE1075 190.72g (b2) BAFL 57.91g Cyclohexanone 1039.82g Methylcyclohexane 207.96g 31.5% 1.05 2.45 0.00202 25800 Production Example 7 (polyimide (1-7)) BisDA-1000 320.00g (b1) PRIAMINE1075 83.08g (b2) BAFL 125.08g Cyclohexanone 908.27g Methylcyclohexane 181.65g 31.5% 1.20 2.45 0.00200 14000 Comparative production example 1 (polyimide (2-1)) BisDA-1000 350.00g (b1) PRIAMINE1075 100.04g (other diamines) 1,3-BAC 61.48g Cyclohexanone 875.00g Methylcyclohexane 145.83g Diethylene glycol dimethyl ether 262.50g 30.2% 1.09 2.50 0.0032 18600

BPAF: 9,9'-bis(3,4-dicarboxyphenoxy) stilbenic dianhydride (trade name "BPAF", manufactured by JFE Chemical Co., Ltd.) BAFL: 9,9'-bis(aminophenyl) fluorine (trade name "BAFL", manufactured by JFE Chemical Co., Ltd.) BisDA-1000: 4,4'-[propane-2,2-diylbis(1,4-phenyleneoxy)]bisphthalic dianhydride (trade name "BisDA-1000", SABIC Innovative Plastics Product made in Japanese contract 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), N,N-diglycidyl-4-glycidoxyaniline (manufactured by Mitsubishi Chemical Corporation, trade name " jER630") 0.35 g, and 1.35 g of toluene as an organic solvent were mixed and thoroughly stirred to obtain an adhesive with a non-volatile content of 30.0%.

Regarding Examples and Comparative Examples other than Example 1, except that the composition of the adhesive was changed as described in Table 2, an adhesive was obtained in the same manner as in Example 1.

[Table 2] Polyimide(1) Crosslinker (2) Organic Solvents (3) non-volatile components Example 1 Polyimide (1-1) 10.00g jER630 0.35g Toluene 1.35g 30.0% Example 2 Polyimide (1-2) 10.00g jER630 0.35g Toluene 1.28g 30.0% Example 3 Polyimide (1-3) 10.00g jER630 0.35g Toluene 1.32g 30.0% Example 4 Polyimide (1-4) 10.00g jER630 0.35g Toluene 1.32g 30.0% Example 5 Polyimide (1-5) 10.00g jER630 0.35g Toluene 1.32g 30.0% Example 6 Polyimide (1-6) 10.00g jER630 0.35g Toluene 1.32g 30.0% Example 7 Polyimide (1-7) 10.00g jER630 0.35g Toluene 1.32g 30.0% Comparative example 1 Polyimide (2-1) 10.00g jER630 0.37g Toluene 0.93g 30.0%

In addition, the organic solvent used when producing a polyimide may also be contained in an 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.; film thickness 12.5 μm; Coefficient of thermal expansion: 15 ppm/° C.) After drying at 180° C. for 3 minutes, an adhesive sheet was obtained.

＜Manufacturing of Copper Clad Laminates＞ A resin-coated copper foil was produced by laminating the adhesive surface of the obtained adhesive sheet on a commercially available electrolytic copper foil (trade name "F2-WS", manufactured by Furukawa Copper Foil Co., Ltd., 18μm thick) from the roughened side.

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

＜Adhesion Test＞ About the obtained copper-clad laminated board, peeling strength (N/cm) was measured based on JIS C 6481 (copper-clad laminated board test method for flexible printed wiring boards). The results are shown in the table.

＜Measurement of dielectric constant and dielectric loss tangent＞ About 7g of the adhesives of Examples and Comparative Examples were injected into fluororesin PFA plates (75mm in diameter, manufactured by Mutual Physical and Chemical Glass Works Co., Ltd.), and heated at 30°C for 10 hours, 70°C for 10 hours, and 100°C. × 6 hours, 120° C. × 6 hours, 150° C. × 6 hours, 180° C. × 12 hours were cured to obtain a resin for measuring a dielectric constant with a film thickness of about 300 μm and a sample of a cured product.

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

[table 3] Adhesive properties Adhesion (N/mm) Solder heat resistance Dielectric constant (10 GHz) Dielectric Loss Tangent (10 GHz) Example 1 1.06 ○ 2.34 0.0030 Example 2 1.05 ○ 2.40 0.0032 Example 3 1.04 ○ 2.44 0.0033 Example 4 1.00 ○ 2.46 0.0092 Example 5 0.95 ○ 2.40 0.0040 Example 6 1.11 ○ 2.45 0.0043 Example 7 0.75 ○ 2.45 0.0042 Comparative example 1 0.80 ○ 2.60 0.0052

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Domestic deposit information (please note in order of depositor, date, and number) none Overseas storage information (please note in order of storage country, institution, date, and number) none

Claims (10)

A kind of polyimide, it is the reactant of monomer group comprising aromatic tetracarboxylic acid anhydride and diamine, and comprises following stilbene group in polymer main chain, and this diamine comprises dimer diamine,

The aforementioned aromatic tetracarboxylic anhydride is 3,3',4,4'-biphenyltetracarboxylic dianhydride, 0 to 5% by mass of diaminopolysiloxane is contained in 100% by mass of the monomer group, and the aforementioned aromatic tetracarboxylic anhydride is The molar ratio of aromatic tetracarboxylic anhydride to the aforementioned diamine is 1.0~1.2, the weight average molecular weight of the polyimide is 5000~50000, and 100 mol% of the aforementioned diamine The content of the diamine component containing the fennel skeleton is 20-80 mole%. An adhesive comprising the polyimide described in claim 1, a crosslinking agent and an organic solvent. A film-like adhesive material comprising a heat-cured product of the adhesive described in Claim 2. An adhesive layer comprising the adhesive described in claim 2, or the film-like adhesive material described in claim 3. An adhesive sheet, comprising the adhesive layer described in claim 4, and a support film. A resin-coated copper foil comprising the adhesive layer described in Claim 4 and copper foil. A copper-clad laminate comprising the resin-coated copper foil described in claim 6, and the copper foil or an insulating sheet. A printed circuit board having a circuit pattern on the copper foil surface of the copper-clad laminate described in Claim 7. A multilayer circuit board, comprising: a printed circuit board (1) or a printed circuit board (1), the adhesive layer described in claim 4, and a printed circuit board (2) or a printed circuit board (2). A method for manufacturing a multilayer circuit board, which includes the following steps 1 and 2: step 1, by making the adhesive described in claim 2 or the film-like adhesive material described in claim 3, and a printed circuit board (1) or at least one side of the printed circuit board (1) is contacted to manufacture a substrate with an adhesive layer; step 2 is to laminate a printed circuit board (2) or a substrate with an adhesive layer on the substrate. A printed circuit board (2) is subjected to a crimping step under heat and pressure.