TW201805337A - Polyimide, polyimide-based adhesive, film-like adhesive material, adhesive layer, adhesive sheet, copper foil with resin, copper-clad laminate and printed wiring board, and multilayer wiring board and method for manufacturing the same - Google Patents

Abstract

To provide a new polyimide exhibiting high storage modulus of rigidity even on a B-stage temperature condition; a new polyimide-based adhesive which is a composition using the polyimide and provides an adhesive layer having good adhesion, heat-resistant adhesiveness, flow controllability and low dielectric characteristics; and a film-like adhesive material obtained by the adhesive. There are provided polyimide (1) which is a reactant of a monomer group containing an aromatic tetracarboxylic acid anhydride (A) and diamine (B) containing dimer diamine (b1) and trimer triamine (b2) so that a mass ratio [(b1)/(b2)] is in a range of 97/3 to 70/30; a polyimide-based adhesive containing the (1) component, a crosslinking agent (2) and an organic solvent (3); and a film-like adhesive material obtained from the polyimide-based adhesive.

Description

Polyimide, polyimide-based adhesive, film-shaped adhesive material, adhesive layer, adhesive sheet, copper foil with resin, copper-clad laminated board and printed wiring board, and multilayer wiring board and manufacturing method thereof

The invention relates to a polyimide, a polyimide-based adhesive, a film-like adhesive material, an adhesive layer, an adhesive sheet, a copper foil with a resin, a copper-clad laminated board and a printed wiring board, and a multilayer wiring board and the like. Production method.

Flexible printed wiring boards (FPWB: Flexible Printed Wiring Board) and printed wiring boards (PWB: Printed Wiring Board), and multi-layer boards (MLB: Multi-Layer Board) derived from them have been widely used in mobile Mobile communication devices such as phones and smartphones, or base station devices, network-related electronic devices such as servers and routers, and products such as large-scale computers.

In recent years, in these products, high-frequency signals are used in order to transmit and process large-capacity messages at high speed, but high-frequency signals are very easy to attenuate. Therefore, the aforementioned multilayer circuit boards and other methods are required to suppress transmission loss. .

As a means of suppressing the transmission loss in a multilayer wiring board, for example, when a printed wiring board or a printed circuit board is laminated, a polyimide-based adhesive is used, which is not only excellent in heat-resistant adhesion, but also has dielectric properties. A characteristic in which both the constant and the dielectric loss tangent are low (hereinafter referred to as low dielectric characteristics) (see, for example, Patent Documents 1 to 3). [Prior Art Literature] (Patent Literature)

Patent Document 1: Japanese Patent Application Laid-Open No. 2009-299040 Patent Document 2: Japanese Patent Application Laid-Open No. 2014-045076 Patent Literature 3: Japanese Patent Application Laid-Open No. 2014-086591

[Problems to be Solved by the Invention] On the other hand, with the miniaturization, thinning, and weight reduction of the aforementioned products, electronic components and semiconductor components have been further miniaturized. In flexible wiring boards equipped with these components, Further high definition and high density have been performed.

In order to obtain a multilayer wiring board having a high-definition / high-density substrate laminated in this manner and having high adhesion reliability, it is necessary to melt the polyimide-based adhesive and / or the polyimide-based film-like adhesive material at a temperature of about 180 ° C. State (B-stage), and spread it across the adherends, that is, the fine unevenness and voids of the printed wiring board and printed circuit board, to ensure wetting, and to form heat-resistant adhesiveness and low dielectric after post-curing Excellent adhesive layer.

In order to improve the wettability of polyimide-based adhesives and / or polyimide-based film-like adhesives in stage B, it is only necessary to reduce the melt viscosity. For example, the main material, polyimide, can be lowered. The molecular weight is increased, or an ether bond or a branched structure is introduced into the molecule, or the molecular end is covered with a low molecule. However, if the melt viscosity is reduced by this method, the adhesive layer will be excessively softened or liquefied under heat and pressure (B-stage, about 180 ° C), and the adhesive will ooze or flow out from the edge of the multilayer circuit board. It may impair the flow controllability, or the heat-resistant adhesiveness and low dielectric properties of the adhesive layer may be reduced.

The problem to be solved by the present invention is to provide a novel polyimide which shows a high storage rigidity modulus even under the temperature condition of the B stage.

The problem to be solved by the present invention is also to provide a novel polyimide-based adhesive, and a film-like adhesive material obtained from the adhesive, an adhesive layer, an adhesive sheet, a copper foil with a resin, and a copper-clad laminate. Board, printed wiring board, multilayer wiring board and manufacturing method thereof, the polyimide-based adhesive is a composition made of the aforementioned polyimide and can obtain an adhesive layer, and the adhesiveness and heat resistance of the adhesive layer Good adhesion, flow control and low dielectric properties. [Technical means to solve the problem]

The present inventors conducted intensive research and found that if a specific polyimide using a diamine component as a raw material, it exhibits a high storage rigidity modulus even under the temperature condition of stage B. The diamine component not only contains Dimer diamine as a diamine component also contains a specific amount of trimer triamine. In addition, it has been found that by using this polyimide, an adhesive and a film-like adhesive material that can solve the aforementioned problems can be obtained.

That is, the present invention relates to polyimide, polyimide-based adhesives, film-like adhesive materials, adhesive layers, adhesive sheets, copper-clad laminated boards and printed wiring boards, and multilayer wiring boards and the following manufacturing methods. method.

上述式中，X表示單鍵、-SO₂ -、-CO-、-O-、-O-C₆ H₄ -C(CH₃ )₂ -C₆ H₄ -O-或-COO-X¹ -OCO-，X¹ 表示-(CH₂ )_l -或-H₂ C-HC(-O-C(=O)-CH₃ ) -CH₂ -，其中，l=1～20。 (項目3) 如上述項目1或2所述之聚醯亞胺(1)，其中，成分(A)與成分(B)的莫耳比為1＜[(A)／(B)]＜1.5。 (項目4) 如上述項目1〜3中任一項所述之聚醯亞胺(1)，其中，前述單體群組進一步包含二胺基聚矽氧烷(b3)。 (項目5) 如上述項目4所述之聚醯亞胺(1)，其中，成分(A)與成分(B)的莫耳比為0.6＜[(A)／(B)]＜1.4。 (項目6) 如上述項目4或5所述之聚醯亞胺(1)，其中，成分(b1)和成分(b2)、與成分(b1)、成分(b2)及成分(b3)的莫耳比為0.3＜[〔(b1)＋(b2)〕／〔(b1)＋(b2)＋(b3)〕]＜1。 (項目7) 一種聚醯亞胺系黏著劑，其含有上述項目中任一項所述之聚醯亞胺(1)、交聯劑(2)及有機溶劑(3)。 (項目8) 如上述項目7所述之聚醯亞胺系黏著劑，其中，前述交聯劑(2)是選自由環氧化合物、苯并噁嗪化合物、雙馬來醯亞胺化合物及氰酸酯化合物所組成之群組中的至少一種。 (項目9) 如上述項目8所述之聚醯亞胺系黏著劑，其中，前述環氧化合物是下述結構的四環氧丙基二胺：

上述式中，Y表示伸苯基或伸環己基(cyclohexylene group)。 (項目10) 如上述項目7〜9中任一項所述之聚醯亞胺系黏著劑，其中，相對於100質量份的成分(1)，以固體成分換算，成分(2)為11～900質量份，並且成分(3)為150～900質量份。 (項目11) 一種薄膜狀黏著材料，其是由上述項目7〜9中任一項所述之聚醯亞胺系黏著劑所獲得。 (項目12) 一種黏著層，其是由上述項目7〜10中任一項所述之聚醯亞胺系黏著劑或上述項目11所述之薄膜狀黏著材料所獲得。 (項目13) 一種黏著薄片，其包含上述項目12所述之黏著層與支撐薄膜。 (項目14) 一種附有樹脂之銅箔，其包含上述項目12所述之黏著層與銅箔。 (項目15) 一種覆銅積層板，其包含上述項目14所述之附有樹脂之銅箔與一銅箔。 (項目16) 一種覆銅積層板，其包含上述項目15所述之附有樹脂之銅箔與一絕緣性薄片。 (項目17) 一種印刷線路板，其是在上述項目15或16所述之覆銅積層板的銅箔面上形成有電路圖案而成。 (項目18) 一種多層線路板，其包含： 芯材也就是一印刷線路板或一印刷電路板、 上述項目12所述之黏著層、及 其他基材也就是一印刷線路板或一印刷電路板。 (項目19) 一種多層線路板的製造方法，其包含下述步驟1和步驟2： 步驟1，是藉由使上述項目7〜10中任一項所述之聚醯亞胺系黏著劑或上述項目11所述之薄膜狀黏著材料，與芯材也就是一印刷線路板或一印刷電路板的至少其中一面接觸，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，積層一印刷線路板或一印刷電路板，並在加熱和加壓下進行壓合的步驟。 [發明的功效](Item 1) A polyimide (1) is a reactant of a monomer group including an aromatic tetracarboxylic anhydride (A) and a diamine (B), wherein the diamine (B) is in a mass ratio ( b1) / (b2) includes dimer diamine (b1) and trimer triamine (b2) so that it is in the range of 97/3 to 70/30. (Item 2) The polyimide (1) according to the above item 1, wherein the component (A) is represented by the following structure:

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- or -COO-X ¹ -OCO -, X ¹ represents-(CH ₂ ) _l -or -H ₂ C-HC (-OC (= O) -CH ₃ ) -CH _2- , wherein l = 1 to 20. (Item 3) The polyimide (1) according to the above item 1 or 2, wherein the molar ratio of the component (A) to the component (B) is 1 <[(A) / (B)] <1.5 . (Item 4) The polyimide (1) according to any one of the items 1 to 3, wherein the monomer group further includes a diamine polysiloxane (b3). (Item 5) The polyimide (1) according to the item 4, wherein the molar ratio of the component (A) to the component (B) is 0.6 <[(A) / (B)] <1.4. (Item 6) The polyimide (1) according to the above item 4 or 5, wherein the component (b1) and the component (b2), and the component (b1), the component (b2), and the component (b3) are The ear ratio is 0.3 <[[(b1) + (b2)] / [(b1) + (b2) + (b3)]] <1. (Item 7) A polyimide-based adhesive containing the polyimide (1), the cross-linking agent (2), and the organic solvent (3) according to any one of the above items. (Item 8) The polyfluorene-based adhesive according to the item 7, wherein the crosslinking agent (2) is selected from the group consisting of an epoxy compound, a benzoxazine compound, a bismaleimide compound, and cyanide. At least one of the group consisting of an ester compound. (Item 9) The polyimide-based adhesive according to the item 8, wherein the epoxy compound is a tetraglycidyldiamine having the following structure:

In the above formula, Y represents a phenylene group or a cyclohexylene group. (Item 10) The polyimide-based pressure-sensitive adhesive according to any one of items 7 to 9, wherein the component (2) is 11 to 100 parts by mass of the component (1) in terms of solid content. 900 parts by mass, and the component (3) is 150 to 900 parts by mass. (Item 11) A film-like adhesive material obtained from the polyimide-based adhesive according to any one of items 7 to 9 above. (Item 12) An adhesive layer obtained from the polyimide-based adhesive according to any one of items 7 to 10 above or the film-like adhesive material according to item 11 above. (Item 13) An adhesive sheet comprising the adhesive layer and the supporting film according to the item 12 above. (Item 14) A copper foil with a resin, comprising the adhesive layer and the copper foil described in Item 12 above. (Item 15) A copper-clad laminated board comprising the copper foil with resin and a copper foil as described in the item 14 above. (Item 16) A copper-clad laminated board comprising the copper foil with resin described in item 15 above and an insulating sheet. (Item 17) A printed wiring board having a circuit pattern formed on a copper foil surface of the copper-clad laminated board according to item 15 or 16 above. (Item 18) A multilayer circuit board comprising: a core material that is a printed circuit board or a printed circuit board, the adhesive layer described in the above item 12, and other substrates that are a printed circuit board or a printed circuit board . (Item 19) A method for manufacturing a multilayer wiring board, which includes the following steps 1 and 2: The step 1 is performed by using the polyimide-based adhesive described in any one of the above items 7 to 10 or the above. The film-shaped adhesive material described in item 11 is a step of manufacturing a substrate with an adhesive layer in contact with a core material, that is, at least one side of a printed wiring board or a printed circuit board; Step 2 is where A printed circuit board or a printed circuit board is laminated on the substrate of the adhesive layer, and the step of laminating is performed under heating and pressure. [Effect of the invention]

The polyfluorene imine (1) of the present invention shows a high storage rigidity modulus even under the temperature condition of the B stage. Therefore, the adhesive obtained by using the polyimide and the film-like adhesive material obtained from the adhesive have fewer cases of the adhesive exuding or flowing out at the B stage, and have heat-resistant adhesiveness and low dielectric properties. Good, so it is particularly suitable for high frequency printed wiring board applications. The high-frequency printed circuit board manufactured by using the adhesive and the adhesive material has a small transmission loss of high-frequency electric signals, and is therefore suitable for, for example, a mobile communication device represented by a smart phone or a mobile phone or a base thereof. Devices, servers, routers, and other network-related electronic devices, mainframe computers, etc.

The polyfluoreneimine (1) (hereinafter referred to as component (1)) of the present invention is a polymer comprising an aromatic tetracarboxylic anhydride (A) (hereinafter referred to as component (A)) and a diamine (B) (Hereinafter referred to as component (B)) as a reaction component, the diamine (B) contains a dimer diamine (b1) / (b2) so that the mass ratio (b1) / (b2) falls within a range of 95/5 to 75/25 ( b1) (hereinafter referred to as component (b1)) and trimer triamine (b2) (hereinafter referred to as component (b2)).

(上述式中，X表示單鍵、-SO₂ -、-CO-、-O-、-O-C₆ H₄ -C(CH₃ )₂ -C₆ H₄ -O-或-COO-X¹ -OCO- (X¹ 表示-(CH₂ )_l -(l=1～20)或-H₂ C-HC(-O-C(=O) -CH₃ )-CH₂ -)。)As component (A), various well-known aromatic tetracarboxylic anhydrides can be used. Specifically, an aromatic tetracarboxylic anhydride represented by the following structure can be used.

(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- or -COO-X ^1- OCO- (X ¹ represents _{- (CH 2) l - (} l = 1 ~ 20) or _{-H 2 C-HC (-OC (} = O) -CH 3) -CH 2 -).)

Specific examples of the component (A) include, for example, pyromellitic dianhydride, 4,4'-oxybis (phthalic anhydride), 3,3 ', 4,4'-diphenyl ketone tetra Formic acid dianhydride, 3,3 ', 4,4'-diphenyl ether tetracarboxylic dianhydride, 3,3', 4,4'-diphenylphosphonium tetracarboxylic dianhydride, 1,2,3,4- Pyromellitic anhydride, 1,4,5,8-naphthalenetetracarboxylic anhydride, 2,3,6,7-naphthalenetetracarboxylic anhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2, 2 ', 3,3'-biphenyltetracarboxylic dianhydride, 2,3,3', 4'-biphenyltetracarboxylic dianhydride, 2,3,3 ', 4'-diphenylketonetetracarboxylic dianhydride , 2,3,3 ', 4'-diphenyl ether tetracarboxylic dianhydride, 2,3,3', 4'-diphenylphosphonium tetracarboxylic dianhydride, 2,2-bis (3,3 ', 4,4'-tetracarboxyphenyl) tetrafluoropropane dianhydride, 2,2'-bis (3,4-dicarboxyphenoxyphenyl) fluorene dianhydride, 2,2-bis (2,3-di Carboxyphenyl) propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, and 4,4 '-[prop-2,2-diylbis (1,4-benzene Alkoxy)] bis (phthalic anhydride), etc .; and two or more of these aromatic tetracarboxylic acids may be combined. Among them, from the viewpoints of the mutual solubility of the component (A) and the component (B), normal-temperature adhesiveness, heat-resistant adhesiveness, and the like, it is preferably at least one selected from the group consisting of: 3, 3 ', 4,4'-diphenylketonetetracarboxylic dianhydride, 4,4'-[propane-2,2-diylbis (1,4-phenyleneoxy)] bis (phthalate Acid anhydride), and 4,4'-oxybis (phthalic anhydride).

The component (b1) is obtained by substituting all carboxyl groups of the dimer of unsaturated fatty acids such as oleic acid, that is, all the carboxyl groups of the dimer acid with primary amine groups (see Japanese Patent Application Laid-Open No. 9-12712, etc.), and may be specially The use of various well-known ingredients is restricted. The non-limiting structural formula of the dimer diamine is shown below (in each structural formula, m + n = 6-17, p + q = 8-19, and a dotted line means a carbon-carbon single bond or a carbon-carbon double bond).

Examples of commercially available components (b1) include: Versamine 551 (manufactured by BASF Corporation of Japan), Versamine 552 (manufactured by Japan Corning Corporation, Versamine 551 hydride), PRIAMINE 1075, and PRIAMINE 1074 (all of Japan) (Made by CRODA Corporation). In addition, the dimer diamine component in these commercially available products is generally about 95 to 98% by mass. The remaining part may include a trimer triamine described later, and it is generally within a range of 2% by mass or less. .

The component (b2) is obtained by substituting all carboxyl groups of terpolymers of unsaturated fatty acids such as oleic acid, that is, trimer acids (refer to Japanese Patent Application Publication No. 2013-505345, etc.) to primary amine groups, and may be specially prepared The use of various well-known ingredients is restricted. The following shows the non-limiting structural formula of the trimer triamine (in each structural formula, m + n = 6 to 17, p + q = 8 to 19, and the dotted line means a carbon-carbon single bond or a carbon-carbon double bond, R It means ethylene (-CH ₂ CH _2- ) or ethylene (-CH = CH-)).

Examples of commercially available products of the component (b1) include PRIAMINE 1071 (manufactured by Nippon Korota Co., Ltd.) and the like. The trimer triamine component in these commercially available products is generally about 15 to 20% by mass, and the dimer diamine may be contained in an amount exceeding 80% by mass as the remainder.

The mass ratio [(b1) / (b2)] of the component (b1) to the component (b2) in the component (B) is about 97/3 to 70/30. By being in the range described above, the balance between the flow controllability and the heat-resistant adhesiveness is made good. From this point of view, the ratio is preferably about 96/4 to 75/25, more preferably about 95/5 to 75/25, even more preferably about 93/7 to 75/25, and most preferably 93/7. ~ 83/17.

The method for preparing the component (B) is not particularly limited. Examples of the method include mixing the aforementioned component (b1) and the ingredient (b2) produced by various known methods so as to achieve the aforementioned mass ratio; or achieving the aforementioned molar ratio. A commercially available product of the component (b1) and a commercially available product of the aforementioned component (b2) are mixed.

Molar ratios of the component (A) and the component (B) are not particularly limited, and from the viewpoint of maintaining a high storage rigidity modulus at a high temperature, generally 1 <[(A) / (B )] <1.5, in general, it is preferably 1.03 ≦ [(A) / (B)] ≦ 1.4, and from the viewpoint of colloidization and the like, it is more preferably 1.07 ≦ [(A) / The degree of (B)] ≦ 1.4 is preferably 1.09 ≦ [(A) / (B)] ≦ 1.16.

In the present invention, the monomer group including the component (A) and the component (B) may include a diamine polysiloxane (hereinafter referred to as a component (b3)). Examples of the component (b3) include 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 [3- (2-Aminophenyl) propyl] polydimethylsiloxane, α, ω-bis [3- (4-aminophenyl) propyl] polydimethylsiloxane, 1 , 3-bis (3-aminopropyl) tetramethyldisilazane, 1,3-bis (4-aminobutyl) tetramethyldisilaxane and the like. Examples of the component (B) other than (b1) to component (b3) include diaminocyclohexane, diaminodicyclohexylmethane, dimethyl-diaminodicyclohexylmethane, and Aminobicyclo [2.2.1] heptane, bis (aminomethyl) -bicyclo [2.2.1] heptane, 3 (4), 8 (9) -bis (aminomethyl) tricyclo [5.2. 1.02,6] alicyclic diamines such as decane, isophorone diamine, 4,4'-diaminodicyclohexylmethane and 1,3-bis (aminomethyl) cyclohexane; 2,2 -Bis (aminophenoxyphenyl) such as bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, etc. ) Propanes; diamino diphenyl ethers such as 3,3'-diamino diphenyl ether, 3,4'-diamino diphenyl ether, 4,4'-diamino diphenyl ether Class; phenylenediamines such as p-phenylenediamine, m-phenylenediamine; 3,3'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4'- Diaminodiphenylsulfide such as diaminodiphenylsulfide; 3,3'-diaminodiphenylphosphonium, 3,4'-diaminodiphenylphosphonium, 4,4'- Diaminodiphenylfluorenes such as diaminodiphenylphosphonium; 3,3'-diaminodiphenylketone; 4,4'-diaminodiphenylketone; 3,4'-diaminodiphenyl ketones and other diaminodiphenyl ketones; 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3, Diaminodiphenylmethanes such as 4'-diaminodiphenylmethane; 2,2-bis (3-aminophenyl) propane, 2,2-bis (4-aminophenyl) propane, Bis (aminophenyl) propanes such as 2- (3-aminophenyl) -2- (4-aminophenyl) propane; 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-amino Phenyl) -2- (4-aminophenyl) -1,1,1,3,3,3-hexafluoropropane and other bis (aminophenyl) hexafluoropropanes; 1,1-bis (3 -Aminophenyl) -1-phenylethane, 1,1-bis (4-aminophenyl) -1-phenylethane, 1- (3-aminophenyl) -1- (4 -Aminophenyl) -1-phenylethane and other bis (aminophenyl) phenylethanes; 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 other bis (aminophenoxy) benzene Class; 1,3-bis (3-aminobenzyl) benzene, 1,3-bis (4-aminobenzyl) benzene, 1,4-bis (3-aminobenzyl) ) Benzene, 1,4-bis (4-aminobenzyl) benzene, etc. Bis (aminobenzyl) benzenes; 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-di Bis (aminodimethyl) benzenes such as methylbenzyl) benzene; 1,3-bis (3-amino-α, α-bis (trifluoromethyl) benzyl) benzene, 1,3 -Bis (4-amino-α, α-bis (trifluoromethyl) benzyl) benzene, 1,4-bis (3-amino-α, α-bis (trifluoromethyl) benzyl ) Benzene, 1,4-bis (4-amino-α, α-bis (trifluoromethyl) benzyl) benzene and other bis (aminobis (trifluoromethyl) benzyl) benzenes; 2 1,6-bis (3-aminophenoxy) benzonitrile, 4,4'-bis (3-aminophenoxy) biphenyl, 4,4'-bis (4-aminophenoxy) Aminophenoxybiphenyls such as biphenyl; amines such as bis [4- (3-aminophenoxy) phenyl] one, bis [4- (4-aminophenoxy) phenyl] one Phenoxyphenyl ketones; bis [4- (3-aminophenoxy) phenyl] sulfide, amine [phenoxyphenyl] sulfide, bis [4- (4-aminophenoxy) phenyl] thioether and other aminophenoxy Phenyl sulfides; bis [4- (3-aminophenoxy) phenyl] fluorene, bis [4- (4-aminophenoxy) phenyl] fluorene and other aminophenoxyphenyl groups Tadpoles; double [4- (3- Aminophenoxyphenyl ethers such as aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] ether; 2,2-bis [4- (3- Aminophenoxy) phenyl] propane, 2,2-bis [3- (3-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2, 2-bis [4- (4-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane and other aminophenoxyphenylpropanes; as other than the above Examples of the component (B) other than (b1) to component (b3) include 1,3-bis [4- (3-aminophenoxy) benzylidene] benzene, 1,3-bis [4- (4-Aminophenoxy) benzylidene] benzene, 1,4-bis [4- (3-aminophenoxy) benzylidene] benzene, 1,4-bis [4 -(4-aminophenoxy) benzylidene] benzene, 1,3-bis [4- (3-aminophenoxy) -α, α-dimethylbenzyl] benzene, 1, 3-bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene, 1,4-bis [4- (3-aminophenoxy) -α, α -Dimethylbenzyl] benzene, 1,4-bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene, 4,4'-bis [4- (4-Aminophenoxy) benzylidene] diphenyl ether, 4,4'-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] di Phenyl ketone, 4,4'-bis [4- (4-amino-α, α-dimethyl Benzyl) phenoxy] diphenylphosphonium, 4,4'-bis [4- (4-aminophenoxy) phenoxy] diphenylphosphonium, 3,3'-diamino-4 , 4'-Diphenoxydiphenylketone, 3,3'-diamino-4,4'-diphenoxydiphenylketone, 3,3'-diamino-4-phenoxy Diphenyl ketone, 3,3'-diamino-4-biphenoxydiphenyl ketone, 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, bis (aminomethyl) ether, bis (2-aminoethyl) ether, bis (3-aminopropyl) ether, bis [(2-aminomethoxy) ethyl ] Ether, bis [2- (2-aminoethoxy) ethyl] ether, bis [2- (3-aminopropyloxy) ethyl] ether, 1,2-bis (aminomethoxy ) Ethane, 1,2-bis (2-aminoethoxy) ethane, 1,2-bis [2- (aminomethoxy) ethoxy] ethane, 1,2-bis [2 -(2-aminoethoxy) ethoxy] ethane, ethylene glycol bis (3-aminopropyl) ether, diethylene glycol bis (3-aminopropyl) ether, triethylene glycol Bis (3-aminopropyl) ether, ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diamine Hexane, 1,7- Aminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12- Diaminododecane, 2,6-bis (3-aminophenoxy) pyridine and the like. Two or more of these components can be combined.

Even when the component (b3) is used, the amount of the component (A) and the component (B) used is not particularly limited. When the component (b3) is used, from the viewpoints of the solubility of the component (1) in an organic solvent to be described later, or the balance between normal temperature adhesiveness, heat-resistant adhesiveness, and low dielectric properties, the component is generally used. The molar ratio of (A) to component (B) is about 0.6 <[(A) / (B)] <1.4, and preferably about 0.8 <[(A) / (B)] <1.2.

(b1) ～ The use ratio of the component (b3) is also not particularly limited. In general, the molar ratio of the component (b1) and the component (b2) to the component (b1), the component (b2), and the component (b3) 0.3 <[[(b1) + (b2)] / [(b1) + (b2) + (b3)]] <1, preferably 0.6 <[[(b1) + (b2)] / [ (b1) + (b2) + (b3)]] <1, more preferably 0.6 <[[(b1) + (b2)] / [(b1) + (b2) + (b3)]] <0.96 Degree.

The component (1) can be produced by various known methods. For example, in general, at a temperature of about 60 to 120 ° C (preferably about 80 to 100 ° C), the component (A) and the component (b1), the component (b2), and the component (b3) as required Component (B) undergoes a polymerization addition reaction for about 0.1 to 2 hours (preferably about 0.1 to 0.5 hours). Then, the obtained polymerized adduct is further subjected to a hydrazidation reaction, that is, a dehydration ring-closure reaction at a temperature of about 80 to 250 ° C, preferably 100 to 200 ° C, for about 0.5 to 50 hours (preferably 1 to 20 hours or so), whereby the target component (1) can be obtained.

In the fluorene imidization reaction, various known reaction catalysts, dehydrating agents, and organic solvents described below can be used. Examples of the reaction catalyst include aliphatic tertiary amines such as triethylamine; aromatic tertiary amines such as dimethylaniline; heterocyclic tertiary amines such as pyridine, methylpyridine, and isoquinoline. ; And two or more of these reaction catalysts can be combined. Examples of the dehydrating agent include aliphatic acid anhydrides such as acetic anhydride and aromatic acid anhydrides such as benzoic anhydride. Two or more of these dehydrating agents may be combined.

The ring closure rate of the fluoreneimine of the component (1) is not particularly limited. Here, the "fluorene imine ring closure ratio" means the content of the cyclic ammine bond in the component (1), and it can be obtained by various spectroscopic means such as nuclear magnetic resonance (NMR) or infrared (IR) spectral analysis. Decide. In addition, the ring closure ratio of the fluoreneimine of the component (1) is generally set to 70% or more, and preferably about 85 to 100%, thereby making room temperature adhesiveness and heat-resistant adhesiveness good.

The physical properties of the component (1) obtained in this manner are not particularly limited. Examples of the upper limit of the glass transition temperature include 250, 200, 150, and 100 ° C. Examples of the lower limit include 90 and 80. , 70, 60, 50, 40, 30, 20 ° C, etc. The range of the glass transition temperature can be appropriately selected from the above-mentioned upper limit and lower limit, etc. From the viewpoint of the balance between normal temperature adhesiveness, heat-resistant adhesiveness, and low dielectric properties, the glass transition temperature is generally About 20 to 250 ° C, preferably about 30 to 200 ° C. The weight average molecular weight is not particularly limited. Examples of the upper limit include: 60,000, 50,000, 40,000, 30,000, 20,000, 10,000, 9000, 8000, 7000, 6000, 5000, and the like. Examples of the lower limit include: : 50000, 40,000, 30,000, 20000, 10000, 9000, 8000, 7000, 6000, 5000, 4000, 3000, etc. For example, the range of weight average molecular weight can be appropriately selected from the above upper limit and lower limit, etc. From the same viewpoint as above, it is generally about 3,000 to 60,000, and preferably about 6,000 to 40,000. For example, the weight average molecular weight can be calculated | required by polystyrene conversion value measured by colloidal permeation chromatography (GPC).

The polyfluorene-based adhesive of the present invention is a composition containing the aforementioned component (1), a cross-linking agent (2) (hereinafter referred to as component (2)), and an organic solvent (3) (hereinafter referred to as component (3)).

As a component (2), if it is a component which can exhibit a performance as a crosslinking agent of a polyimide, various well-known components can be used without a restriction | limiting in particular. Specifically, for example, at least one selected from the group consisting of an epoxy compound, a benzoxazine compound, a bismaleimide compound, and a cyanate ester compound is preferred.

Examples of the epoxy compound include a phenol novolac epoxy compound, a cresol novolac epoxy compound, a bisphenol A epoxy compound, a bisphenol F epoxy compound, and a bisphenol S epoxy compound. , Hydrogenated bisphenol A type epoxy compound, hydrogenated bisphenol F type epoxy compound, diphenylethylene type epoxy compound, epoxy compound containing triazine skeleton, epoxy compound containing fluorene skeleton, linear aliphatic ring Oxygen compounds, alicyclic epoxy compounds, epoxypropylamine type epoxy compounds, triphenol methane type epoxy compounds, alkyl modified triphenol methane type epoxy compounds, biphenyl type epoxy compounds, dicyclopentyl Diene skeleton epoxy compounds, naphthalene skeleton-containing epoxy compounds, aryl alkane type epoxy compounds, tetraglycidyl xylene diamine, modified epoxy resins modified with dimer acid Epoxy compounds, dipropylene acid dimer acid, etc .; and two or more kinds can be combined. Examples of commercially available products include "jER828" or "jER834" and "jER807" manufactured by Mitsubishi Chemical Corporation; "ST-3000" manufactured by Nippon Steel Chemical Co., Ltd .; and Daicel Chemical Industry Co., Ltd. "CELLOXIDE 2021P" manufactured by Co., Ltd .; "YD-172-X75" manufactured by Nippon Steel Chemical Co., Ltd .; "TETRAD-X" manufactured by Mitsubishi Gas Chemical Co., Ltd., etc. Among them, at least one selected from the group consisting of a bisphenol A-type epoxy compound, a bisphenol, and the like from the viewpoint of the balance of heat-resistant adhesiveness, moisture-resistant solder heat resistance, and low dielectric properties. A phenol F type epoxy compound, a hydrogenated bisphenol A type epoxy compound, and an alicyclic epoxy compound.

(式中，Y表示伸苯基或伸環己基)In particular, the tetraglycidyldiamine of the following structure has good compatibility with the component (1). Moreover, if this tetraglycidyl xylylene diamine is used, it will become easy to make a low loss elastic modulus of an adhesive layer, and it will also be excellent in heat resistance adhesiveness and low dielectric characteristics.

(Where Y represents phenylene or cyclohexyl)

When an epoxy compound is used as the component (2), various known hardeners for epoxy compounds can be used in combination. Specific examples include succinic anhydride, phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, and 3-methyl-hexahydrophthalic acid. Formic anhydride, 4-methyl-hexahydrophthalic anhydride, or a mixture of 4-methyl-hexahydrophthalic anhydride and hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyl -Tetrahydrophthalic anhydride, nadic anhydride, methylnadic anhydride, norbornane-2,3-dicarboxylic anhydride, methylnorbornane-2,3-dicarboxylic anhydride, formic acid Anhydride hardeners such as cyclohexene dicarboxylic anhydride, 3-dodecenyl succinic anhydride, and octenyl succinic anhydride; dicyandiamine (DICY), aromatic diamine (trade names "LonzacureM-DEA", " "LonzacureM-DETDA", etc. are made by Lonza Japan Ltd.), amine hardeners such as aliphatic amines; phenol novolac resin, cresol novolac resin, bisphenol A novolac resin, triazine modified phenol novolac Resin, phenolic hydroxyl-containing phosphazene (trade name "SPH-100" manufactured by Otsuka Chemical Co., Ltd.), and other phenolic hardeners and rings Phosphoazene-based compounds; rosin-based cross-linking agents such as maleic acid modified rosin or its hydride; and two or more of them can be combined. Among them, a phenol-based hardener is preferred, and a phenolic hydroxyl-containing phosphazene-based hardener is particularly preferred. The use amount of these hardeners is not particularly limited. Generally, when the solid content of the adhesive of the present invention is 100% by mass, it is about 0.1 to 120% by mass, preferably about 10 to 40% by mass. .

When an epoxy compound is used as the component (2) and the aforementioned hardener is used, a reaction catalyst may be used. Specific examples include 1,8-diaza-bicyclo [5.4.0] undec-7-ene, triethylenediamine, benzyldimethylamine, triethanolamine, and dimethylamine. Tertiary amines such as ethyl alcohol, gins (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 tetraphenylborate (tetraphenyl phosphonium tetraphenylborate), tetrabenzene Tetraphenylborates such as 2-ethyl-4-methylimidazole and tetraphenylboronic acid N-methylmorpholine, etc .; and two or more of them may be combined. The amount of the reaction catalyst used is not particularly limited. Generally, when the solid content of the adhesive of the present invention is 100% by mass, it is about 0.01 to 5% by mass.

Examples of the benzoxazine compound include 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), etc .; and two or more of them can be combined. Furthermore, a phenyl group, a methyl group, a cyclohexyl group, or the like may be bonded to the nitrogen of the oxazine ring. Examples of commercially available products include "Benzoxazine F-a" or "Benzoxazine P-d" manufactured by Shikoku Chemical Industry Co., Ltd., and "RLV-100" manufactured by Air Water.

Examples of the bismaleimide compound include 4,4'-diphenylmethane bismaleimide, m-phenylene bismaleimide, and bisphenol A diphenyl ether bismaleimide. Lyme imine, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene Bismaleimide, 1,6'-bismaleimide- (2,2,4-trimethyl) hexane, 4,4'-diphenyl ether bismaleimide, 4,4'-diphenylpyrenebismaleimide, etc .; and two or more kinds can be combined. Examples of commercially available products include "BAF-BMI" manufactured by JFE Chemical Co., Ltd. and the like.

Examples of the cyanate compound include 2-allylphenol cyanate, 4-methoxyphenol cyanate, and 2,2-bis (4-cyanophenol) -1,1,1 , 3,3,3-hexafluoropropane, bisphenol A cyanate, diallyl bisphenol A cyanate, 4-phenylphenol cyanate, 1,1,1-ginseng (4-cyanate Phenyl) ethane, 4-cumylphenol cyanate, 1,1-bis (4-cyanophenyl) ethane, 4,4'-bisphenol cyanate, and 2,2 -Bis (4-cyanophenyl) propane and the like; and two or more kinds can be combined. Moreover, as a commercial item, "PRIMASET BTP-6020S (made by Japan Lonsa Co., Ltd.)" etc. are mentioned, for example.

As the component (3), various known organic solvents can be used. Specific examples include N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, dimethylmethylene, N-methylcaprolactam, and methyltrimethylpyrrolidone. Aprotic polar solutions such as glycol dimethyl ether and methyl diglyme; or alicyclic solvents such as cyclohexanone and methyl cyclohexane; methanol, ethanol, propanol, benzyl alcohol, cresol Alcohol-based solvents; aromatic solvents, such as toluene; and two or more of these organic solvents may be combined. The amount of the organic solvent used is not particularly limited. Generally, the solid content of the resin composition of the present invention is in a range of about 10 to 60% by mass.

The amount of the component (1), the component (2), and the component (3) in the polyfluorene-based adhesive of the present invention is not particularly limited, and it is converted to a solid content with respect to 100 parts by mass of the component (1). Examples of the upper limit of the component (2) include: 60, 50, 40, 30, 20, 10 parts by mass, and the like; and examples of the lower limit include: 50, 40, 30, 20, 10, 5, 3 , 2 parts by mass, etc .; as examples of the upper limit of component (3), 900, 800, 700, 600, 500, 400, 300 parts by mass, etc .; as examples of the lower limit, 300, 250, 200, 150 parts by mass. For example, the upper limit and lower limit may be selected to set the range of the component (2) and the component (3), and the handleability, heat resistance, electrical characteristics, adhesiveness, etc. during coating may be used as the adhesive. From the viewpoint of the balance of physical properties, generally, the component (2) is about 2 to 60 parts by mass, preferably about 3 to 40 parts by mass, with respect to 100 parts by mass of the component (1), and the ingredient ( 3) It is about 150 to 900 parts by mass, preferably about 200 to 500 parts by mass.

The polyfluorene-based adhesive of the present invention is obtained, for example, by dissolving the component (1) and the component (2) in the component (3). In addition, the aforementioned ring-opening esterification reaction catalyst or dehydrating agent, plasticizer, weathering agent, antioxidant, heat stabilizer, lubricant, antistatic agent, whitening agent, colorant, and conductive agent may be blended as necessary. , Release agents, surface treatment agents, viscosity modifiers, phosphorus flame retardants, flame retardant fillers, silicon dioxide fillers, and fluorine fillers and other additives.

The film-like adhesive material of the present invention is an article obtained from the polyimide-based adhesive of the present invention. Specifically, it is obtained, for example, by applying this adhesive to an appropriate support, heating it to volatilize the component (3), hardening it, and then peeling it off from this support. The thickness of the adhesive material is not particularly limited, but is generally about 3 to 40 μm. Examples of the support include the following supports.

The adhesive sheet of the present invention is an article, and its constituent elements include: an adhesive layer obtained from the polyimide-based adhesive of the present invention or the film-shaped adhesive material of the present invention; and a support film. Examples of the support include the following plastic films: polyester, polyimide, polyimide-silica dioxide mixture, polyethylene, polypropylene, polyethylene terephthalate, and polynaphthalene Ethylene formate, polymethyl methacrylate resin, polystyrene resin, polycarbonate resin, acrylonitrile-butadiene-styrene resin, ethylene terephthalate, or phenol, phthalic acid , Aromatic polyester resins such as hydroxynaphthoic acid and p-hydroxybenzoic acid (so-called liquid crystal polymers, "Vecstar" manufactured by Kuraray Co., Ltd.) and the like. Moreover, when apply | coating the polyfluorene imide-type adhesive of this invention to this support body, the said coating means can be employ | adopted. The thickness of the coating layer is also not particularly limited. Generally, the thickness of the coating layer may be in a range of about 1 to 100 μm after drying, and preferably in a range of about 3 to 50 μm. The adhesive layer of the adhesive sheet can be protected by a protective film.

The copper foil with resin of the present invention is an article, and its constituent elements include the adhesive layer and the copper foil of the present invention. Specifically, it is obtained by coating or sticking the polyfluorene-based adhesive or the film-shaped adhesive on a copper foil. Examples of the copper foil include a rolled copper foil and an electrolytic copper foil. The thickness is not particularly limited, but is generally about 1 to 100 μm, and preferably about 2 to 38 μm. The copper foil may be a copper foil subjected to various surface treatments (roughening, rust prevention, etc.). Examples of the rust prevention treatment include a plating treatment using a plating solution containing nickel, zinc, tin, or the like, or a so-called mirror finish treatment such as a chromate treatment. Examples of the coating means include the aforementioned methods. The adhesive layer of the resin-coated copper foil may be uncured, or may be an adhesive layer that is partially or completely cured by heating. The partially hardened adhesive layer is in a state called a so-called B-stage. The thickness of the adhesive layer is not particularly limited, but is generally about 0.5 to 3.0 μm. Further, the copper foil can be further bonded to the adhesive surface of the resin-coated copper foil to form a copper foil with resin on both sides.

The copper-clad laminated board of the present invention is an article, which is formed by bonding the copper foil with resin of the present invention and a copper foil or an insulating sheet, and is also referred to as a copper clad laminate (CCL) . Specifically, it is obtained by pressing the resin-coated copper foil of the present invention on at least one side or both sides of various known copper foils or insulating sheets under heating. When bonded to one surface, the resin-coated copper foil of the present invention may be pressed to the other surface. The number of resin-coated copper foils and insulating sheets in the copper-clad laminated board is not particularly limited. The insulating sheet is preferably a prepreg. A prepreg is a sheet-like material obtained by impregnating a reinforcing material such as glass cloth with a resin and hardening 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 polyaramide resins are generally used. The thickness of the prepreg is not particularly limited, but is generally about 20 to 500 μm. The heating and pressing conditions are not particularly limited, but are generally about 150 to 280 ° C (preferably about 170 ° C to 240 ° C) and about 0.5 to 20MPa (preferably about 1 to 8MPa).

The printed wiring board of the present invention is an article obtained by forming a circuit pattern on a copper foil surface of the copper-clad laminated board of the present invention. Examples of the patterning method include a subtractive method and a semi-additive method. As the semi-additive method, for example, the following method can be mentioned: patterning with a resist film on the copper foil surface of the copper-clad laminated board of the present invention, then performing electrolytic copper plating, removing the resist, and then using an alkaline solution Etching. The thickness of the circuit pattern layer in the printed wiring board is not particularly limited. In addition, a multilayer substrate can also be obtained by using the printed wiring board as a core material and laminating the same printed wiring board, or other known printed wiring boards or printed circuit boards. In the lamination, in addition to the polyimide-based adhesive of the present invention, other known polyimide-based adhesives can also be used. The number of layers in the multilayer substrate is not particularly limited. In addition, through-holes can be inserted each time, and the inside can be plated. The line width / pitch ratio of the circuit pattern is not particularly limited, but is generally about 1 μm / 1 μm to 100 μm / 100 μm. The height of the circuit pattern is not particularly limited, but is generally about 1 to 50 μm.

The multilayer circuit board of the present invention is an article, and its constituent elements include: a core material that is a printed circuit board or a printed circuit board, an adhesive layer of the present invention, and other substrates that are a printed circuit board or a printed circuit board. A printed circuit board. The printed circuit board or printed circuit board may be the printed circuit board or printed circuit board of the present invention, and may also be a known printed circuit board or printed circuit board.

The multilayer wiring board of the present invention can be obtained by a manufacturing method including the following steps 1 and 2. In step 1, the polyimide-based adhesive or film-like adhesive material of the present invention is brought into contact with a core material, that is, at least one side of a printed circuit board or a printed circuit board, to produce an adhesive layer. Substrate steps. Step 2 is a step of laminating a printed circuit board or a printed circuit board on the substrate with an adhesive layer, and performing lamination under heating and pressure.

The printed circuit board or printed circuit board may be the printed circuit board or printed circuit board of the present invention, and may also be a known printed circuit board or printed circuit board.

In step 1, the means for bringing the polyfluorene-based adhesive or film-like adhesive material of the present invention into contact with the adherend is not particularly limited, and various known coating means such as a curtain coater, Roll coater, laminator, laminator, etc.

The heating temperature and the pressing time in step 2 are not particularly limited. Generally speaking, it is preferred that: (a) at least one of the polyimide-based adhesive or film-like adhesive material of the present invention and the core material is used; After one side contact, it is generally heated to about 70 to 200 ° C, and it takes about 1 to 10 minutes to carry out the hardening reaction. (B) Then further heat treatment is performed to make the hardening reaction of component (2) proceed. This heat treatment The conditions are generally about 150 ° C to 250 ° C, and about 10 minutes to 3 hours. The pressure is not particularly limited, and it is generally about 0.5 to 20 MPa, and preferably about 1 to 8 MPa for the entire steps (a) and (b). [Example]

Hereinafter, the present invention will be specifically described through examples and comparative examples, but the scope of the present invention is not limited to these examples and comparative examples. In each case, parts and% are based on mass unless otherwise specified.

<Production of Polyimide> (Production Example 1) 300.00 g of 4,4 '-[propyl-2,2-diylbis ( 1,4-phenyleneoxy)] bis (phthalic anhydride) (trade name "BisDA-1000", manufactured by SABIC Innovative Plastics Japan LLC.), Hereinafter abbreviated as BisDA), 1042.73 g of cyclohexanone, and 208.55 g of methylcyclohexane, and heated to 60 ° C. Then, 289.36 g of a commercially available trimer triamine (trade name "PRIAMINE1071", trimer triamine / dimer diamine mass ratio = 20/80, manufactured by Koroda Co., Ltd.) was added dropwise. It took 12 hours at 140 ° C. to carry out the fluorene imidization reaction, thereby obtaining a solution of polyfluorene (1-1) (non-volatile content 31.9%). The molar ratio of the acid component / amine component of the polyimide was 1.13.

Production Examples other than Production Example 1 and Comparative Production Examples were performed by changing the composition of the resin solution as described in Table 1, and were carried out in the same manner as in Production Example 1 to obtain polyimide. For example, Comparative Manufacturing Example 1 was performed according to the following procedure.

(Comparative Production Example 1) In the same reaction vessel as in Production Example 1, 310.00 g of BisDA, 992.00 g of cyclohexanone, and 124.00 g of methylcyclohexane were charged and heated to 60 ° C. Then, 306.59 g of a commercially available dimer diamine (trade name “PRIAMINE 1075”) was added slowly, and the mass ratio of the trimer triamine / dimer diamine was 2/98, manufactured by Koroda Co., Ltd. ), It was heated to 140 ° C., and it took 12 hours to carry out the fluorene imidization reaction, thereby obtaining polyfluorene imine (2-1) (non-volatile content 35.7%). The molar ratio of the acid component / amine component of this polyimide was 1.05.

[Table 1] BisDA-1000‧‧‧4,4 '-[propyl-2,2-diylbis (1,4-phenyleneoxy)] bis (phthalic anhydride). Manufactured by SABIC Innovative Plastics Japan Co., Ltd. PRIAMINE1071 ‧ ‧ ‧ trimer triamine / dimer diamine mass ratio = 20/80, manufactured by Japan Croda Corporation. PRIAMINE 1075 ‧ ‧ ‧ trimer triamine / dimer diamine mass ratio = 2/98, manufactured by Japan Croda Corporation.

<Measurement of Storage Rigidity Modulus> The solutions of Production Example 1 and Comparative Production Example 1 were applied to NAFLON PTFE tape No. 9001 (manufactured by Nicus Corporation), and dried at room temperature for 12 hours. It dried at 150 degreeC for 5 minutes, and produced the adhesive sheet of about 20 micrometers.

Then, the adhesive sheet was folded to make a sheet having a thickness of about 300 μm, and then a commercially available viscoelasticity measuring device (ARES-2KSTD-FCO-STD, manufactured by Rheometric Scientific, Inc.) was used to measure the temperature dependence of the storage rigidity modulus. Sex. The temperature increase rate was 10 ° C / min. The results are shown in Fig. 1.

(Example 1) A solution of 100.00 g of a polyimide resin (1-1), a solution of 22.34 g of a polyimide resin (2-1), and 0.82 g of bisphenol A as a component (2) were mixed. Type epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd., trade name "jER828", epoxy equivalent 190g / eq), 3.61g of hydroxyl-containing polyphenylene ether (trade name "SA90", SABIC Innovative Plastics Japan Limited) Manufactured by a responsible company, a hydroxyl equivalent of 840 g / eq) and 21.11 g of toluene as an organic solvent (3), and uniformly stirred to obtain a resin composition having a nonvolatile content of 30.0%.

The examples and comparative examples other than Example 1 were performed in the same manner as in Example 1 except that the composition of the adhesive was changed as described in Table 2. For example, Comparative Example 1 is performed according to the following procedure.

(Comparative Example 1) A solution of 100.00 g of polyimide resin (2-1) and 0.73 g of bisphenol A-type epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd., trade name as component (2)) were mixed. "JER828", epoxy equivalent 190 g / eq), 3.24 g of hydroxyl-containing polyphenylene ether (trade name "SA90", manufactured by SABIC Innovative Plastics Japan Co., Ltd., hydroxyl equivalent 840 g / eq), and organic solvents 28.24 g of toluene was stirred uniformly, thereby obtaining a resin composition having a nonvolatile content of 30.0%.

[Table 2] The organic solvent (3) may include an organic solvent used in the production of polyimide. SG-708-6: an acrylic elastomer manufactured by Nagase ChemteX Corporation.

<Production of Adhesive Sheet> The adhesive composition of Example 1 was applied to the block copolymerized polyimide-oxidized so that the thickness after drying was 20 μm and the left and right edges were each 1 cm. Silicon hybrid film (trade name "POMIRAN N25", manufactured by Arakawa Chemical Industries, Ltd., thermal expansion coefficient = 18 ppm, tensile modulus of elasticity = 5.9 GPa, film thickness 25 μm, width 10 cm, length 15 cm), and dried at 180 ° C. 3 Minutes, to thereby obtain an adhesive sheet.

<Creating a copper-clad laminated board> A film sheet having a width of 10 cm and a length of 4 cm was cut from the adhesive sheet in a direction perpendicular to the direction in which the gap coating was performed. Next, an adhesive surface of the thin film sheet was laminated on the mirror side of a commercially available electrolytic copper foil (trade name "F2-WS", manufactured by Furukawa Copper Foil Co., Ltd., 18 μm in thickness, 10 cm in width, and 5 cm in length) to prepare a test. sample. A schematic diagram of a test sample is shown in FIG. 1.

Then, the test sample was placed on a support for pressure, and the support was obtained from the same material by heating and pressing from above at a pressure of 5 MPa, 170 ° C, and 30 minutes, thereby producing a laminate. film.

1. Adhesion test The peel strength (N / cm) of the copper-clad laminated board was measured in accordance with Japanese Industrial Standard (JIS) C 6481 (Test method for copper-clad laminated board for flexible printed wiring boards). The results are shown in Table 3.

2. Solder heat resistance test The copper-clad laminate was floated in a solder bath at 288 ° C for 30 seconds with the copper foil side facing downward, and it was confirmed whether there was a change in appearance. The no change was set to ○, and the case where there was foaming or swelling was set to x. The results are shown in Table 3.

3. Evaluation of the flow controllability After visual inspection of the right end of the adhesive layer (hardened layer) in the laminated film, it was confirmed that there was no change in the position of the rear end portion before heating and pressing. That is, even if this hardened layer is heated and pressurized, it does not flow out (0 mm) in the horizontal direction, and it can be seen that the flow controllability is good. The results are shown in Table 3.

<Preparation of hardened material sample for measurement of dielectric constant> Approximately 7 g of the adhesive composition of Example 1 was poured into a fluororesin PFA flat disk (75 mm in diameter, manufactured by Hikari Glass Co., Ltd.), and the temperature was 30 ° C. 10 The hardened sample for the dielectric constant measurement having a film thickness of about 300 μm was obtained by curing at conditions of 10 hours at 70 ° C., 6 hours at 100 ° C., 6 hours at 120 ° C., 6 hours at 150 ° C., and 12 hours at 180 ° C.

Then, according to JIS C2565, a commercially available dielectric constant measuring device (cavity resonator type, manufactured by AET Corporation) was used to measure the dielectric constant and dielectric loss tangent at 10 GHz of the cured sample. The results are shown in Table 3.

Tests 1 to 3 were also performed on the adhesive composition of Comparative Example 1 in the same manner. In Test 3, it was confirmed that the horizontal direction of POMIRAN N25 in the laminated film for testing was about 2 mm, and a hardened layer flowed out in a gentle wave shape.

[table 3]

1‧‧‧ insulating film
2‧‧‧ Adhesive layer
3‧‧‧ copper foil

FIG. 1 is a graph showing temperature changes in storage rigidity modulus of the polyfluorene imine (1-1) in Production Example 1 and the polyfluorene imine (1-2) in Comparative Example 1. FIG. Fig. 2 is a schematic diagram of a sample for a flow control test; further, in Fig. 2, reference numeral 1 represents an insulating film (block copolymerized polyfluorene imide-silica mixed film), and reference numeral 2 represents an adhesive layer of the present invention. Reference numeral 3 denotes a copper foil.

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Claims (19)

A polyimide (1) is a reactant comprising a monomer group of an aromatic tetracarboxylic anhydride (A) and a diamine (B), wherein the diamine (B) has a mass ratio (b1) / ( b2) The dimer diamine (b1) and the trimer triamine (b2) are included in the range of 97/3 to 70/30. The polyimide (1) according to claim 1, wherein the component (A) is represented by the following structure:

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- or -COO-X ¹ -OCO -, X ¹ represents-(CH ₂ ) _l -or -H ₂ C-HC (-OC (= O) -CH ₃ ) -CH _2- , where l = 1 to 20. The polyimide (1) according to claim 1 or 2, wherein the molar ratio of the component (A) to the component (B) is 1 <[(A) / (B)] <1.5. The polyfluoreneimide (1) according to any one of claims 1 to 3, wherein the monomer group further includes a diamine polysiloxane (b3). The polyimide (1) according to claim 4, wherein the molar ratio of the component (A) to the component (B) is 0.6 <[(A) / (B)] <1.4. The polyimide (1) according to claim 4 or 5, wherein the molar ratio of the component (b1) and the component (b2) to the component (b1), the component (b2), and the component (b3) is 0.3. <[[(B1) + (b2)] / [(b1) + (b2) + (b3)]] <1. A polyimide-based adhesive containing the polyimide (1), a cross-linking agent (2), and an organic solvent (3) according to any one of claims 1 to 6. The polyfluorene-based adhesive according to claim 7, wherein the crosslinking agent (2) is selected from the group consisting of an epoxy compound, a benzoxazine compound, a bismaleimide compound, and a cyanate ester compound. At least one of the group consisting. The polyimide-based adhesive according to claim 8, wherein the epoxy compound is a tetraglycidyldiamine having the following structure:

In the above formula, Y represents phenylene or cyclohexyl. The polyimide-based adhesive according to any one of claims 7 to 9, wherein, based on 100 parts by mass of the component (1), in terms of solid content, the component (2) is 11 to 900 parts by mass, In addition, the component (3) is 150 to 900 parts by mass. A thin film-shaped adhesive material obtained from the polyimide-based adhesive according to any one of claims 7 to 10. An adhesive layer obtained from the polyimide-based adhesive according to any one of claims 7 to 10 or the film-like adhesive material according to claim 11. An adhesive sheet comprising the adhesive layer and the supporting film according to claim 12. A copper foil with a resin comprising the adhesive layer and the copper foil according to claim 12. A copper-clad laminated board includes the copper foil with resin described in claim 14 and a copper foil. A copper-clad laminated board comprising the copper foil with resin described in claim 15 and an insulating sheet. A printed wiring board is formed by forming a circuit pattern on a copper foil surface of a copper-clad laminated board according to claim 15 or 16. A multilayer circuit board includes: a core material, that is, a printed circuit board or a printed circuit board, the adhesive layer described in claim 12, and other substrates, that is, a printed circuit board or a printed circuit board. A method for manufacturing a multilayer wiring board, which includes the following steps 1 and 2: The step 1 is performed by using the polyimide-based adhesive according to any one of claims 7 to 10 or claim 11. The film-shaped adhesive material is in contact with the core material, that is, at least one side of a printed circuit board or a printed circuit board, to produce a substrate with an adhesive layer; Step 2 is the substrate with the adhesive layer On a substrate, a printed circuit board or a printed circuit board is laminated, and the step of laminating is performed under heating and pressure.