TW202219124A - Polyimide, adhesive, film-like adhesive, adhesion 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

To provide a polyimide, an adhesive, a film-like adhesive, an adhesion layer, an adhesive sheet, a copper foil with resin, a copper-clad laminate, a printed wiring board, and a multilayer wiring board and a method of producing the same. The present invention provides: a polyimide that is a reactant of a monomer group containing an aromatic tetracarboxylic acid anhydride and a diamine containing a dimer diamine, and has a fluorenylene group in the polymer main chain; an adhesive containing the polyimide, a crosslinker and an organic solvent; and a film-like adhesive, an adhesion layer, an adhesive sheet, a copper foil with resin, a copper-clad laminate, a printed wiring board, and a multilayer wiring board and a method of producing the same.

Description

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

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

Various known adhesives have been used to manufacture mobile communication devices such as mobile phones and smartphones, base station devices, network-related electronic devices such as servers and routers, and printed circuit boards included in mainframe computers.

The present applicant proposes "a polyimide-based adhesive composition comprising a polyimide resin, a thermosetting resin, a flame retardant and an organic solvent, wherein the polyimide resin is made of aromatic tetracarboxylic acids and containing 30 mol% or more of specific dimer diamines react with diamines" (refer to Patent Document 1). [Prior Art Literature] (patent literature)

Patent Document 1: Japanese Patent No. 5534378

[Problems to be Solved by Invention] In recent years, in the above-mentioned network-related electronic equipment, it is necessary to transmit and process large-capacity information at high speed with low loss, and the electrical signals processed by the printed wiring boards of these products are also increasing in frequency. High-frequency electrical signals tend to be attenuated, 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 properties) are required for adhesives generally used in printed wiring boards.

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

As a result of intensive research, the present inventors 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。 The present disclosure provides the following items. (Item 1) A polyimide, which is a reactant of a monomer group comprising an aromatic tetracarboxylic anhydride and a diamine, and which comprises the following phenylene group in a polymer main chain, the diamine comprising a dimer diamine,

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

In the above formula, any one of R ¹ and R ² represents a group having an amine group, the other one 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 , 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 a diamine-based polysiloxane. (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 and 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 epoxide, benzoxazine, bismaleimide and cyanate ester . (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 a phenylene group or a cyclohexylene group. (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-hardened 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 item. (Item 11) An adhesive sheet comprising the adhesive layer described in the above item, and a support film. (Item 12) A resin-attached copper foil, comprising the adhesive layer described in the above-mentioned item, and a copper foil. (Item 13) A copper clad laminate comprising the resin-attached copper foil described in the above item, and the copper foil. (Item 14) A copper-clad laminate comprising the resin-attached 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 circuit board (2). (Item 17) A method for manufacturing a multilayer wiring board, comprising 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 item 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 circuit board (2) or printed circuit board (2), and perform 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 those indicated in the above-mentioned combinations. [Effect of invention]

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

In the entire specification of the present disclosure, the ranges of numerical values such as physical property values and contents can be appropriately set (for example, selected from the upper limit 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, etc., 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. .

。 [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 phenylene group in the polymer main chain, the Diamines include dimer diamines,

.

In the present disclosure, "containing a phenylene group in the main chain of the polymer" means that a phenylene group is included in the longest chain constituting the polymer.

<Aromatic tetracarboxylic anhydride> Aromatic tetracarboxylic acid anhydrides can be used individually or in 2 or more types. The aromatic tetracarboxylic anhydride may, for example, be a perylene skeleton-containing tetracarboxylic anhydride, a symmetrical aromatic tetracarboxylic anhydride, or 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 pyrene skeleton) In one embodiment, the tetracarboxylic anhydride containing a pyrene skeleton is represented by the following general formula:

In the above formula, any one of R ¹ and R ² represents a group with an acid anhydride group, the other one 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 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 which has an acid anhydride group, a 3, 4- dicarboxyphenoxy group, a 3, 4- dicarboxy phenyl group, etc. are illustrated.

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

Examples of the alkyl group include straight-chain alkyl groups, branched alkyl groups, and cycloalkyl groups.

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

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

As a branched alkyl group, an isopropyl group, an isobutyl group, an isopentyl group, an isohexyl group, an isodecyl group, etc. are illustrated.

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 branched alkyl groups (groups exemplified above, etc.).

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

The tetracarboxylic acid anhydride containing a perylene skeleton is exemplified by: 9,9'-bis[4-(3,4-dicarboxyphenoxy)phenyl]perylene dianhydride, 9,9'-bis(3,4- Dicarboxyphenoxy) fornic acid dianhydride and the like.

The upper limit of the content of the perylene skeleton-containing tetracarboxylic anhydride in 100 mol % of the aromatic tetracarboxylic anhydride can be exemplified as follows: 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 of the embodiments, the content of the tetracarboxylic anhydride containing a perylene skeleton in 100 mol % of the aromatic tetracarboxylic anhydride is preferably about 0 to 100 mol %, more preferably about 50 to 100 mol %.

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

The upper limit of the content of the tetracarboxylic anhydride containing a pyrene skeleton in 100 mol % of the monomer group can be exemplified as follows: 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 of the embodiments, the content of the tetracarboxylic anhydride containing a perylene skeleton in 100 mol % of the monomer group is preferably about 0-75 mol %.

The upper limit of the content of the perylene skeleton-containing tetracarboxylic anhydride in 100 mass % of the monomer group can be exemplified as follows: 75 mass %, 70 mass %, 60 mass %, 50 mass %, 40 mass %, 30 mass %, 20 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 perylene skeleton-containing tetracarboxylic anhydride 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。 (Symmetrical Aromatic Tetracarboxylic Anhydride) In the present disclosure, "symmetrical aromatic tetracarboxylic anhydride" means an aromatic tetracarboxylic anhydride having a symmetry axis (eg, C2 symmetry axis) in the molecule. Symmetrical aromatic tetracarboxylic anhydrides, such as those represented by the following general formulas, can be exemplified,

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.

Symmetrical aromatic tetracarboxylic anhydrides represented by the above general formula include 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenyltetracarboxylic 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)stilbene dianhydride, 2, 2',3,3'-biphenyltetracarboxylic dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, pyromellitic dianhydride, 1,2,3,4- Benzenetetracarboxylic anhydride, 1,4,5,8-naphthalenetetracarboxylic anhydride, 2,3,6,7-naphthalenetetracarboxylic anhydride, etc.

Among the above-mentioned symmetrical aromatic tetracarboxylic anhydrides, those selected from the group consisting of 3,3', 4,4' are preferably selected from the viewpoints of compatibility between the aromatic tetracarboxylic anhydride and diamine, room temperature adhesiveness, and heat-resistant adhesiveness. - 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 oxydiphthalic anhydride.

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

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

The upper limit of the content of the symmetrical aromatic tetracarboxylic anhydride in 100 mass % of the monomer group can be exemplified as follows: 75 mass %, 70 mass %, 60 mass %, 50 mass %, 40 mass %, 30 mass %, 20 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 %, 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) that are neither the above-mentioned perylene 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 as follows: 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 acid anhydrides in the aromatic tetracarboxylic anhydride can be, for example, 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 mass %, about 0 mass %, and the like.

In one embodiment, the content of other acid anhydrides in the monomer group can be exemplified as follows: 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 as follows: 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 the aromatic tetracarboxylic anhydride in 100 mol % of the monomer group can be exemplified as follows: 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 anhydride in 100 mol % of the monomer group is preferably about 50-75 mol %.

The upper limit of the content of the aromatic tetracarboxylic anhydride in 100% by mass of the monomer group can be exemplified by: 75% by mass, 70% by mass, 65% by mass, 60% by mass, 55% by mass, etc. The lower limit can be exemplified by: 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＞ The diamines can be used alone or in two or more kinds. The diamine may, for example, be dimer diamine, diamine containing a perylene skeleton, diamine polysiloxane, or the like.

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

Commercially available dimer diamines include Versamine 551 (manufactured by Nippon Corning Co., Ltd.), Versamine 552 (manufactured by Nippon Corning Co., Ltd.; hydrogenated product of Versamine 551), PRIAMINE 1075, and PRIAMINE 1074 (all in Japan). Manufactured by Koluoda Co., Ltd.), etc.

The upper limit of the content of the dimer diamine component in 100 mol % of diamine can be exemplified as follows: 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, the content of the dimer diamine component in 100 mol % of diamine is preferably about 20 to 100 mol % from the viewpoint of improving flexibility, tackiness, and solvent solubility.

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

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

The upper limit of the content of the dimer diamine in 100 mass % of the monomer group can be exemplified: 50 mass %, 40 mass %, 30 mass %, 20 mass %, 10 mass %, 8 mass %, etc.; the lower limit can be exemplified : 40 mass %, 30 mass %, 20 mass %, 10 mass %, 8 mass %, 5 mass %, etc. In one embodiment, the content of the 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 pyrene skeleton) In one embodiment, the diamine containing pyrene skeleton is represented by the following general formula,

In the formula, either 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 either one of R ³ and R ⁴ represents a group having an amine 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 amine group" means a group in which at least one hydrogen atom in an amine group and a functional group is substituted with an amine group. The group having an amino group may, for example, be an amino group, an alkylamino group, an arylamino group, an alkoxyamino group, an aryloxyamino group, or the like.

The aryl group may 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 with a straight-chain or branched alkyl group.

As a monocyclic aryl group, a phenyl group, a tolyl group, a mesityl group and the like can be exemplified. Moreover, as a condensed-ring aryl group, a naphthyl group etc. are illustrated.

Examples of diamines containing a pyrene skeleton include: 9,9'-bis(aminophenyl)pyrene, 9,9'-bis(4-amino-3-methylphenyl)pyrene, 9,9'- Bis(4-amino-3-fluorophenyl) fluoride, 9,9'-bis(4-amino-3-hydroxyphenyl) fluoride, 9,9'-bis(4-methyl-3-amine) phenyl) fluoride, 9,9'-bis(4-fluoro-3-aminophenyl) fluoride, 9,9'-bis(4-hydroxy-3-aminophenyl) fluoride, 9,9' -Bis[4-(4-aminophenoxy)phenyl]pyrene, etc.

The upper limit of the content of the diamine skeleton-containing diamine component in 100 mol % of diamine can be exemplified as follows: 80 mol %, 70 mol %, 60 mol %, 50 mol %, 40 mol %, 30 mol % %, 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% and so on. In one embodiment, from the viewpoint of improving the dielectric properties, the content of the perylene skeleton-containing diamine component in 100 mol % of the diamine is preferably about 20 to 80 mol %.

The upper limit of the content of the perylene skeleton-containing diamine component in 100% by mass of the 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 as follows: 75% by mass, 70% by mass, 60% by mass, 50% by mass, 40% by mass, 30% by mass, 25% by mass, 20% by mass, and the like. In one embodiment, from the viewpoint of improving the dielectric properties, the content of the diamine component containing a pyrene skeleton in 100 mol % of the diamine is preferably about 20 to 80 mass %.

The upper limit of the content of the diamine containing a pyrene skeleton in 100 mol % of the monomer group can be exemplified as follows: 50 mol %, 40 mol %, 30 mol %, 20 mol %, 10 mol %, 5 The lower limit can be exemplified by 40 mol%, 30 mol%, 20 mol%, 10 mol%, 5 mol%, 0 mol%, and the like. In one embodiment, the content of the diamine containing a perylene skeleton in 100 mol % of the monomer group is preferably 0-50 mol %.

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

The upper limit of the ratio of the substance amount of the perylene skeleton-containing diamine to the amount of the dimer diamine (diamine containing the perylene skeleton/dimer diamine) can be exemplified by: 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 and the like. In one embodiment, from the viewpoint of improving flexibility, adhesiveness, and dielectric properties, the ratio of the amount of the perylene skeleton-containing diamine to the amount of the dimer diamine (the perylene skeleton-containing diamine /dimer diamine), preferably about 0.25 to 4.00.

(Diaminopolysiloxane) Diaminopolysiloxane, exemplified by: α,ω-bis(2-aminoethyl)polydimethylsiloxane, α,ω-bis(3-aminopropyl)polydimethylsiloxane Oxane, α,ω-Bis(4-aminobutyl)dimethylsiloxane, α,ω-Bis(5-aminopentyl)dimethylsiloxane, α,ω-bis [3-(2-aminophenyl)propyl]dimethylsiloxane, α,ω-bis[3-(4-aminophenyl)propyl]dimethylsiloxane, 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 as follows: 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 the diamine polysiloxane in 100 mol % of the diamine is preferably about 0 to 5 mol % from the viewpoint of improving flexibility.

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

The upper limit of the content of diamine polysiloxane in 100 mol % of the monomer group can be exemplified as follows: 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 the diamine polysiloxane in 100 mol % of the monomer group is preferably about 0 to 5 mol %.

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

(other diamines) In one of the embodiments, the monomer group may contain diamines other than the above (also referred to as other diamines). Other diamines can be exemplified by: alicyclic diamine, bisaminophenoxyphenylpropane, diaminodiphenyl ether, phenylenediamine, diaminodiphenyl sulfide, diaminodiphenyl Diamine, diaminobenzophenone, diaminodiphenylmethane, diaminophenylpropane, diaminophenylhexafluoropropane, diaminophenylphenylethane, bisaminophenoxy 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, 4,4'-bis[amine phenoxyphenoxy] diphenyl benzene, 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, extension Alkyl diamines, etc.

Alicyclic diamines include diaminocyclohexane, diaminodicyclohexylmethane, dimethyldiaminodicyclohexylmethane, diaminobicyclo[2.2.1]heptane, bis(amine) ylmethyl)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-bisaminomethylcyclohexane, etc.

Bisaminophenoxyphenylpropane, 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy) base) phenyl] propane and the like.

Diaminodiphenyl ether, 3, 3'- diamino diphenyl ether, 3, 4'- diamino diphenyl ether, 4, 4'- diamino diphenyl ether, etc. are illustrated. .

The phenylenediamine may, for example, be phenylenediamines such as p-phenylenediamine and m-phenylenediamine.

Diaminodiphenyl sulfide, 3, 3'- diamino diphenyl sulfide, 3, 4'- diamino diphenyl sulfide, 4, 4'- diamino diphenyl thioether, etc.

Diaminodiphenylsene, such as 3,3'-diaminodiphenylsene, 3,4'-diaminodiphenylsene, 4,4'-diaminodiphenylsene, etc. can be illustrated. .

For diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, etc. can be illustrated. .

Diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, etc. are illustrated. .

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

Diaminophenylhexafluoropropane, 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, 1,1-bis(3-aminophenyl)-1-phenylethane, 1,1-bis(4-aminophenyl)-1- Phenylethane, 1-(3-aminophenyl)-1-(4-aminophenyl)-1-phenylethane, etc.

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

Bisaminobenzylbenzene, 1,3-bis(3-aminobenzyl)benzene, 1,3-bis(4-aminobenzyl)benzene, 1,4- Bis(3-aminobenzyl)benzene, 1,4-bis(4-aminobenzyl)benzene, and the like.

Bisaminodimethylbenzylbenzene, 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, etc.

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

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

Examples of the aminophenoxyphenylsene include bis[4-(3-aminophenoxy)phenyl]sene, bis[4-(4-aminophenoxy)phenyl]ssene, and the like.

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

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

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

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

Bis[amino-α,α-dimethylbenzylphenoxy]diphenyl benzene, exemplified by: 4,4'-bis[4-(4-amino-α,α-dimethylbenzene Methyl)phenoxy]diphenylene and the like.

4,4'-bis[aminophenoxyphenoxy]diphenylsene, exemplified by: 4,4'-bis[4-(4-aminophenoxy)phenoxy]diphenylsene Wait.

Diaminodiaryloxybenzophenone, 3,3'-diamino-4,4'-diphenoxybenzophenone, 3,3'-diamino-4, 4'-diphenyloxybenzophenone, etc.

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

6,6'-bis(aminoaryloxy)-3,3,3',3'-tetramethyl-1,1'-spirobisindane, 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.

Bis(aminoalkyl)ether, bis(aminomethyl)ether, bis(2-aminoethyl)ether, bis(3-aminopropyl)ether, etc. are illustrated.

Bis(aminoalkoxyalkyl)ether, bis[2-(aminomethoxy)ethyl]ether, bis[2-(2-aminoethoxy)ethyl]ether, bis[2-(2-aminoethoxy)ethyl]ether, [2-(3-aminopropoxy)ethyl]ether, etc.

The bis(aminoalkoxy)alkane may, for example, be 1,2-bis(aminomethoxy)ethane, 1,2-bis(2-aminoethoxy)ethane, or the like.

Bis[(aminoalkoxy)alkoxy]alkane, 1,2-bis[2-(aminomethoxy)ethoxy]ethane, 1,2-bis[2-(2 -aminoethoxy)ethoxy]ethane, etc.

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

Bis(aminoaryloxy)pyridine, 2,6-bis(3-aminophenoxy)pyridine etc. are illustrated.

Alkylenediamine, ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane Alkane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminodecane Monoalkane, 1,12-diaminododecane, etc.

In one embodiment, the content of other diamines in the diamine can be exemplified as follows: 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 as follows: 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 mass %, about 0 mass %, and the like.

In one embodiment, the content of other diamines in the monomer group can be exemplified as follows: 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 as follows: 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 mass %, about 0 mass %, and the like.

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

The upper limit of the content of the diamine in 100% by mass of the monomer group can be exemplified by: 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 and 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 the aromatic tetracarboxylic anhydride and the 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 and 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 the aromatic tetracarboxylic anhydride to the 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 (also referred to as other monomers) that are neither aromatic tetracarboxylic anhydrides nor diamines. As other monomers, aliphatic tetracarboxylic anhydrides, etc. can be illustrated.

In one embodiment, the content of other monomers in the monomer group can be exemplified as follows: 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 as follows: 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 mass %, about 0 mass %, and the like.

<Physical properties of polyimide, etc.> The upper limit of the weight average molecular weight of the polyimide may, for example, be 50,000, 40,000, 30,000, 20,000, 10,000, 7500, 5,500, and the like; 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 by: 40000, 30000, 20000, 10000, 7500, 5000, 3000, etc.; . In one embodiment, the number-average molecular weight of the polyimide is preferably 2,000 to 40,000 from the viewpoint of dielectric properties, solvent solubility, and flexibility.

The weight-average molecular weight and the number-average molecular weight can be determined as polystyrene-equivalent values measured by, for example, gel permeation chromatography (GPC).

The upper limit of the softening point of the polyimide can be exemplified by: 220°C, 200°C, 150°C, 100°C, 50°C, 25°C, etc.; °C, 25 °C, 20 °C, etc. In one embodiment, from the viewpoint 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 by using a commercially available measuring device (“ARES-2KSTD-FCO-STD” manufactured by Rheometric Scientific Corporation) or the like.

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

In addition, in the step of carrying out the imidization reaction, various well-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 kinds. Examples of the reaction catalyst include aliphatic tertiary amines such as triethylamine; aromatic tertiary amines such as dimethylaniline; and heterocyclic tertiary amines such as pyridine, picoline, and isoquinoline. In addition, as a dehydrating agent, aliphatic acid anhydrides, such as acetic anhydride, aromatic acid anhydrides, such as benzoic anhydride, etc. can be illustrated.

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

[adhesive] The present disclosure provides an adhesive comprising the above-mentioned polyimide, a cross-linking agent and an organic solvent.

The upper limit of the content of the polyimide in 100% by mass of the adhesive can be exemplified as follows: 90% by mass, 80% by mass, 70% by mass, 60% by mass, 50% by mass, 40% by mass, 30% by mass, 20% by mass mass %, 10 mass %, etc.; the lower limit can be exemplified: 80 mass %, 70 mass %, 60 mass %, 50 mass %, 40 mass %, 30 mass %, 20 mass %, 10 mass %, 5 mass %, and the like. As for content of the said polyimide in 100 mass % of the said adhesive agents, it is preferable that it is about 5-90 mass %.

＜Crosslinking agent＞ As long as the crosslinking agent can function as a crosslinking agent of polyimide, various known crosslinking agents can be used without particular limitation. The crosslinking agent may be used alone or in two or more kinds. The crosslinking agent is preferably at least one selected from the group consisting of epoxide, benzoxazine, bismaleimide and cyanate ester.

(epoxide) Examples of epoxides include: phenol novolac type epoxide, cresol novolac type epoxide, bisphenol A type epoxide, bisphenol F type epoxide, bisphenol S type epoxide, hydrogenated bisphenol A Phenol A type epoxide, hydrogenated bisphenol F type epoxide, stilbene type epoxide, epoxide containing triazine skeleton, epoxide containing pyrene skeleton, linear aliphatic epoxide , Alicyclic epoxide, glycidylamine type epoxide, trisphenol methane type epoxide, alkyl modified trisphenol methane type epoxide, biphenyl type epoxide, containing dicyclopentane Diene skeleton epoxides, naphthalene skeleton-containing epoxides, arylalkylene epoxides, tetraglycidyl xylylenediamine, dimer acid modified products of the above epoxides Polymer acid modified epoxide, dimer acid diglycidyl ester, etc. In addition, commercial products of epoxides 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 Kogyo 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, those selected from the group consisting of bisphenol A-type epoxies, bisphenol F-type epoxies, and hydrogenated bisphenol-A-type epoxides are preferred. At least one of the group consisting of epoxide and alicyclic epoxide.

上述式中，Y表示伸苯基或伸環己基。 In particular, tetraglycidyldiamine of the following structure has good compatibility with the above-mentioned 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 favorable.

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

When an epoxide is used as a crosslinking agent, various well-known hardeners for epoxides can be used together. The curing agent for epoxides may be used alone or in two or more kinds. Examples of curing agents 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, methyltetrahydrophthalic anhydride Hydrophthalic anhydride, nadic anhydride, methyl nadic anhydride, norbornane-2,3-dicarboxylic anhydride, methyl norbornane-2,3-dicarboxylic anhydride, methyl ring Acid anhydride hardeners such as hexenedicarboxylic anhydride, 3-dodecenyl succinic anhydride, and octenyl succinic anhydride; dicyandiamide (DICY), aromatic diamines (trade names "LonzacureM-DEA", "LonzacureM-DETDA") ", etc., all are amine-based hardeners such as Lonza Japan Co., Ltd.), aliphatic amines; phenol novolac resin, cresol novolak resin, bisphenol A novolak resin, triazine modified phenol novolak resin, Phenolic hardeners such as phosphazene containing a phenolic hydroxyl group (trade name "SPH-100" manufactured by Otsuka Chemical Co., Ltd., etc.), cyclic phosphazene compounds; maleic acid-modified rosin or its hydrides, etc. Rosin-based cross-linking agent, etc. Among them, a phenol-based hardener is preferable, and a phenolic hydroxyl group-containing phosphazene-based hardener is particularly preferable. The usage-amount of a hardening agent is not specifically limited, When making the solid content of the said adhesive agent into 100 mass %, it is about 0.1-120 mass % preferably, More preferably, it is about 10-40 mass %.

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

(benzoxazine) Benzoxazine, exemplified by: 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. In addition, 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 include "benzoxazine F-a type" or "benzoxazine P-d type" manufactured by Shikoku Chemical Industry Co., Ltd., "RLV-100 manufactured by AIR WATER" "Wait.

(bismaleimide) Bismaleimide, for example: 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 Imide, 1,6'-bismaleimide-(2,2,4-trimethyl)hexane, 4,4'-diphenyl ether bismaleimide, 4,4' - Diphenyl bismaleimide, etc. Moreover, as a commercial item of bismaleimide, "BAF-BMI" by JFE Chemical Co., Ltd. etc. can be illustrated.

(cyanate ester) Cyanate, exemplified by: 2-allylphenol cyanate, 4-methoxyphenol cyanate, 2,2-bis(4-cyanoxyphenol)-1,1,1,3,3 ,3-Hexafluoropropane, Bisphenol A Cyanate, Diallyl Bisphenol A Cyanate, 4-Phenyl Phenol Cyanate, 1,1,1-Sham (4-cyanophenyl) Ethane, 4-isopropylphenylphenol cyanate, 1,1-bis(4-cyanoxyphenyl)ethane, 4,4'-bisphenol cyanate and 2,2-bis(4- cyanophenyl) propane, etc. In addition, as a commercial item of a cyanate ester, "PRIMASET BTP-6020S (made by Lonza Japan Co., Ltd.)" etc. can be illustrated.

In the above-mentioned adhesive, the upper limit of the content of the crosslinking agent relative to 100 parts by mass (in terms of solid content) of the above-mentioned polyimide 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, 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, and the like. 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 above-mentioned polyimide.

The upper limit of the content of the crosslinking agent in 100% by mass of the above-mentioned adhesive can be exemplified as follows: 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 mass %, etc.; the lower limit can be exemplified: 70 mass %, 60 mass %, 50 mass %, 40 mass %, 30 mass %, 20 mass %, 10 mass %, 5 mass %, 2 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 two or more kinds. The organic solvent can be exemplified by N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, dimethylsulfoxide, N-methylcaprolactamide, triethylene glycol dimethyl amide aprotic polar solvents such as methyltriglyme and methyldiglyme; or alicyclic solvents such as cyclohexanone and methylcyclohexane; methanol, ethanol, propanol, benzyl alcohol, methyl alcohol Alcohol-based solvents such as phenol; aromatic solvents such as toluene, and the like.

Further, the content of the organic solvent in the adhesive is not particularly limited, but is preferably an amount in which the solid content mass is 10 to 60 mass % with respect to 100 mass % of the adhesive.

In the above-mentioned adhesive, the upper limit of the content of the organic solvent with respect to 100 parts by mass (in terms of solid content) of the above-mentioned polyimide 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 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 copies 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.

＜Flammability Agent＞ In one embodiment, the above-mentioned adhesive contains a flame retardant. The flame retardant can be used alone or in two or more kinds. Examples of the flame retardant include phosphorus-based flame retardants, inorganic fillers, and the like.

(Phosphorus-based flame retardant (phosphorus-containing flame retardant)) Examples of the phosphorus-based flame retardant include polyphosphoric acid, phosphoric acid ester, phosphazene derivatives that do not contain a phenolic hydroxyl group, and the like. Among the phosphazene derivatives, cyclic phosphazene derivatives are preferred from the viewpoints of flame retardancy, heat resistance, bleeding resistance, and the like. 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 fillers include silica fillers, phosphorus-based fillers, fluorine-based fillers, inorganic ion exchanger fillers, and the like. Commercially available products include FB-3SDC by Denka Co., Ltd., Exolit OP935 by Clariant Chemical Co., Ltd., KTL-500F by Kitamura Co., Ltd., IXE by Toagosei Co., Ltd., and the like.

In the above-mentioned adhesive, the upper limit of the content of the flame retardant relative to 100 parts by mass (in terms of solid content) of the polyimide can be exemplified as follows: 150 parts by mass, 100 parts by mass, 50 parts by mass, 10 parts by mass, 5 parts by mass Parts by mass, etc.; the lower limit can be exemplified by: 125 parts by mass, 100 parts by mass, 50 parts by mass, 10 parts by mass, 5 parts by mass, 1 part by mass, and the like. 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 compound> In one embodiment, the above-mentioned adhesive further contains Z-Si(R ¹ ) _a (OR ² ) _3-a (in the formula, Z represents a compound containing and an acid anhydride) A group of a functional group that reacts with radicals, 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. Reactive alkoxy group represented by Silicon based compounds. The use of the reactive alkoxysilicon compound 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 suppress the exudation of the hardened layer from the end of the base material while improving the interfacial adhesion between the adhesive layer and the base material (so-called anchor effect).

As the reactive functional group contained in Z of the above general formula, an amine group, an epoxy group, a thiol group, and the like can be exemplified.

Compounds in which Z contains an amino group can be exemplified by N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-amino Propyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane and 3-ureidopropyltrialkoxysilane, etc. As a compound whose Z contains an epoxy group, for example, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, - Glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane and 3-glycidoxypropyltriethoxysilane, etc. As the compound in which Z contains a thiol group, for example, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and 3-mercaptopropyl 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 relative to 100 parts by mass (in terms of solid content) of the polyimide can be exemplified as follows: 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, and the like. 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 any substances other than the above-mentioned polyimide, crosslinking agent, organic solvent, flame retardant, and reactive alkoxysilyl compound as an additive.

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

In one embodiment, the content of the additive with respect to 100 parts by mass of the adhesive may be, for example, 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, with respect to 100 parts by mass (in terms of solid content) of the above-mentioned polyimide, 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, 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 an additive in an organic solvent.

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

[adhesive layer] The present disclosure provides an adhesive layer comprising an adhesive or the above-mentioned film-like adhesive material. When producing 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, you may use together the said film-shaped adhesive material and various well-known film-shaped adhesive materials other than the said film-shaped adhesive material.

[adhesive sheet] The present disclosure provides an adhesive sheet comprising the above-mentioned adhesive layer and a support film.

The supporting film can be exemplified by a plastic film. Plastic, exemplified: polyester, polyimide, polyimide-silicon dioxide blend, 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 resins obtained from formic acid (so-called liquid crystal polymers, "Vecstar" manufactured by Kuraray Co., Ltd., etc.) and the like.

In addition, when the said adhesive agent is apply|coated to this support film, the said application|coating means can be used. The thickness of the coating layer is also not particularly limited, but the thickness after drying is preferably about 1 μm to 100 μm, and 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 resin-attached copper foil, which includes the above-mentioned adhesive layer and the copper foil. Specifically, the above-mentioned resin-attached copper foil is a material obtained by coating or attaching the adhesive or the film-like adhesive material to the copper foil. As this copper foil, a rolled copper foil and an electrolytic copper foil can be illustrated. The thickness is not particularly limited, but is preferably about 1 μm to 100 μm, more preferably about 2 μm to 38 μm. Moreover, the copper foil which performed various surface treatments (roughening, rust prevention, etc.) may be sufficient as this copper foil. The anti-rust treatment includes so-called mirror treatment such as plating treatment and chromate treatment performed using a plating solution containing nickel (Ni), zinc (Zn), tin (Sn), or the like. Moreover, as a coating means, the above-mentioned method can be illustrated.

In addition, the adhesive layer of the resin-attached copper foil can be an unhardened adhesive layer, and can also be a partially hardened or fully hardened adhesive layer 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 also not particularly limited, but is preferably about 0.5 μm to 30 μm. Moreover, you may further bond a copper foil to the adhesive surface of this copper foil with resin, and can make the copper foil with resin of double-sided copper foil.

[Copper clad laminate] The present disclosure provides a copper-clad laminate comprising the above-mentioned 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 obtained by press-bonding the above-mentioned copper foil with resin under heating to at least one side or both sides of various known copper foils or insulating sheets. 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 sheets of the resin-attached copper foil and the insulating sheet in the copper-clad laminate is not particularly limited.

In one embodiment, the insulating sheet is preferably a prepreg. The prepreg refers to a sheet-like material obtained by impregnating a reinforcing material such as glass cloth with resin and curing it to a B stage (Japanese Industrial Standard (JIS) C 5603). As the resin, insulating resins such as polyimide resin, phenol resin, epoxy resin, polyester resin, liquid crystal polymer, and aromatic polyamide resin can be used. The thickness of the prepreg is not particularly limited, but is preferably about 20 μm to 500 μm. In addition, the 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 Wiring Board] The present disclosure provides a printed circuit board having circuit patterns on the copper foil surface of the copper-clad laminate. The patterning means for forming the circuit pattern on the copper foil surface of the copper-clad laminate can be exemplified by the subtractive method and the semi-additive method. As the semi-additive method, after patterning with a resist film on the copper foil surface of the copper-clad laminate, electrolytic copper plating is performed, the resist is removed, and the etching is performed with an alkaline solution. 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 build-up printed wiring boards thereon. At the time of lamination, the above-mentioned adhesive agent and other known adhesives other than the above-mentioned adhesive agent may be used in combination. In addition, the number of build-up layers in the multilayer substrate is not particularly limited. In addition, each time the layers are stacked, through holes can be inserted, and the inside can be plated. The line width/line spacing ratio of the circuit pattern is not particularly limited, but is preferably about 1 μm/1 μm to 100 μm/100 μm. Moreover, the height of the said circuit pattern is not specifically limited, either, Preferably it is about 1 micrometer - 50 micrometers.

[Multilayer circuit board] The present disclosure provides a multilayer circuit board, comprising 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. Similarly, 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. Similarly, the printed circuit board (1) and the printed circuit board (2) may be the same or different.

[Manufacturing method of multilayer wiring board] The present 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 substrate with an adhesive layer by bringing the above-mentioned adhesive or the above-mentioned film-like adhesive material into contact with at least one side of the printed circuit board (1) or 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 base material with the 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. Similarly, 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 above-mentioned adhesive or film-like adhesive material into contact with the adherend is not particularly limited, and examples include various known coating means, curtain coaters, roll coaters, and laminators. , pressing machine, etc.

The heating temperature and crimping time in step 2 are not particularly limited, but preferably: (i) after the adhesive or film-like adhesive material of the present invention is brought into contact with at least one side of the core substrate, the temperature is heated to 70°C to 200°C Then, (ii) in order 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 is preferably about 0.5 MPa to 20 MPa, more preferably about 1 MPa to 8 MPa, during the entire period of steps (i) and (ii). [Example]

Hereinafter, the present invention will be specifically described by way of Examples and Comparative Examples. However, the description of 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 only limited to the scope of the patent application. In addition, in each Example and a comparative example, unless otherwise stated, the numerical value, such as a part, %, is a mass basis.

＜Production of polyimide＞ (Manufacturing example 1) 9,9'-bis[4-(3,4-dicarboxyphenoxy)phenyl]fornic acid dianhydride (trade name "BPF -PA", manufactured by JFE Chemical Co., Ltd. hereinafter referred to as BPF-PA) 290.00 g, 980.20 g of cyclohexanone, and 196.04 g of methylcyclohexane, and heated 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 A solution of amine (1-1) (31.6% non-volatile content). 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 carried out 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] (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) Diamine 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)fornic acid dianhydride (trade name "BPAF", manufactured by JFE Chemical Co., Ltd.) BAFL: 9,9'-bis(aminophenyl) fluoride (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 Made by a 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 Co., Ltd., trade name "" jER630") 0.35 g and 1.35 g of toluene as an organic solvent were mixed and stirred sufficiently to obtain an adhesive with a nonvolatile content of 30.0%.

In Examples and Comparative Examples other than Example 1, except that the composition of the adhesive was changed as described in Table 2, it was carried out in the same manner as in Example 1 to obtain an adhesive.

[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 at the time of manufacture of polyimide may be contained in an organic solvent.

＜Production 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 by a gap coater so that the thickness after drying was 20 μm; Coefficient of thermal expansion: 15 ppm/°C), the adhesive sheet was obtained by drying at 180°C for 3 minutes.

<Production of copper clad laminate> The 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., 18 μm thick) on the roughened side.

Next, the obtained copper foil with resin was placed on a 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 makes a copper clad laminate.

＜Adhesion test＞ The peeling strength (N/cm) of the obtained copper clad laminate was measured according to JIS C 6481 (a copper clad laminate test method for flexible printed wiring boards). The results are shown in the table.

<Measurement of dielectric constant and dielectric loss tangent> About 7 g of the adhesives of Examples and Comparative Examples were respectively poured into fluororesin PFA plates (75 mm in diameter, manufactured by Mutual Chemical Glass Co., Ltd.), and heated at 30°C for 10 hours, 70°C for 10 hours, and 100°C. By curing under the conditions of × 6 hours, 120° C. × 6 hours, 150° C. × 6 hours, and 180° C. × 12 hours, a resin and a cured product sample having a film thickness of about 300 μm for dielectric constant measurement were obtained.

Next, with respect to the obtained resin and cured product samples for dielectric constant measurement, 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. and the 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 storage information (please note in the order of storage institution, date and number) none Foreign deposit information (please note in the order of deposit country, institution, date and number) none

Claims (10)

A polyimide, which is a reactant of a monomer group comprising an aromatic tetracarboxylic anhydride and a diamine, and comprises the following indene group in the polymer backbone, the diamine comprising a dimer diamine,

The aromatic tetracarboxylic anhydride is 3,3',4,4'-biphenyltetracarboxylic dianhydride, and 0 to 5 mass % of diamine polysiloxane is contained in 100 mass % of the monomer group, and the aromatic 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 of claim 1, a crosslinking agent and an organic solvent. A film-like adhesive material comprising a heat-hardened product of the adhesive according to claim 2. An adhesive layer comprising the adhesive of claim 2 or the film-like adhesive material of claim 3. An adhesive sheet, comprising the adhesive layer described in claim 4, and a support film. A resin-attached copper foil, comprising the adhesive layer described in claim 4, and a copper foil. A copper-clad laminate comprising the resin-attached copper foil according to claim 6, and the copper foil or insulating sheet. A printed wiring board having a circuit pattern on the copper foil surface of the copper-clad laminate according to claim 7. A multilayer circuit board, comprising: A printed circuit board (1) or a printed circuit board (1), the adhesive layer of claim 4, and a printed circuit board (2) or a printed circuit board (2). A method for manufacturing a multilayer circuit board, comprising the following steps 1 and 2: Step 1 is to make the adhesive according to claim 2, or the film-like adhesive material according to claim 3, in contact with at least one side of the printed circuit board (1) or the printed circuit board (1), to manufacture the step of attaching the substrate with the adhesive layer; Step 2 is a step of laminating a printed circuit board (2) or a printed circuit board (2) on the base material with the adhesive layer, and performing crimping under heating and pressure.