TWI777950B - 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 producing the same - Google Patents

Abstract

The problem to be solved by the present invention is to provide a novel polyimide, and to provide a novel polyimide-based adhesive and a film-like adhesive material obtained from the adhesive. Under the temperature condition of the B stage, it also shows a high storage rigidity modulus. The polyimide-based adhesive is a composition formed by using the polyimide, and an adhesive layer can be obtained. The adhesiveness of the adhesive layer, Good thermal adhesion, flow control and low dielectric properties. The solution of the present invention is a polyimide (1), a polyimide-based adhesive containing the component (1), a crosslinking agent (2) and an organic solvent (3), and the polyimide The film-like adhesive material obtained as an adhesive, the polyimide (1) is a reactant of a monomer group comprising an aromatic tetracarboxylic anhydride (A) and a diamine (B), wherein the diamine ( B) dimer diamine (b1) and trimer triamine (b2) are contained so that mass ratio (b1)/(b2) may be in the range of 97/3-70/30.

Description

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 producing the same

The present invention relates to a polyimide, a polyimide-based adhesive, a film-like adhesive material, an adhesive layer, an adhesive sheet, a resin-attached copper foil, a copper-clad laminate and a printed circuit board, as well as a multilayer circuit board and the like. Manufacturing method.

Flexible Printed Wiring Board (FPWB: Flexible Printed Wiring Board), Printed Wiring Board (PWB: Printed Wiring Board), and Multi-Layer Board (MLB: Multi-Layer Board) obtained by using these have been widely used in action Mobile communication devices such as telephones and smartphones, base station devices, network-related electronic devices such as servers/routers, and large computers.

In recent years, in these products, in order to transmit and process large-capacity information at high speed, high-frequency electrical signals are used, but high-frequency signals are easily attenuated. Therefore, means for suppressing transmission loss are also required for the above-mentioned multilayer circuit boards. .

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

Patent Document 1: JP 2009-299040 A Patent Document 2: JP 2014-045076 A Patent Document 3: JP 2014-086591 A

On the other hand, with the miniaturization, thinning, and weight reduction of the aforementioned products, electronic parts and semiconductor parts have been further miniaturized, and in the flexible circuit boards on which these parts are mounted, further high-definition and high density.

In order to obtain such a multilayer wiring board with high-definition/high-density substrates laminated and with high adhesion reliability, it is necessary to melt the polyimide-based adhesive and/or the polyimide-based film-like adhesive at a temperature of about 180°C. state (B stage), and make it throughout the adherend, that is, the printed circuit board and the fine asperities and voids of the printed circuit board, to ensure wetting, and to form heat-resistant adhesion and low dielectric after post-curing Adhesive layer with excellent properties.

In order to improve the wettability of the B-stage polyimide-based adhesive and/or polyimide-based film-like adhesive material, it is sufficient to reduce the melt viscosity. Molecularization, introduction of ether bonds, branched structures, etc. into the molecule, or covering of molecular ends with low molecular weight. However, if the melt viscosity is reduced in this way, the adhesive layer will be softened or liquefied excessively under heat and pressure (B stage, about 180°C), and the adhesive may ooze or flow out from the edge of the multilayer wiring board. Impaired flow control, or reduced thermal adhesion and low dielectric properties of the adhesive layer.

The problem to be solved by the present invention is to provide a novel polyimide which exhibits a high storage stiffness modulus even under the temperature conditions 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, an adhesive layer, an adhesive sheet, a resin-attached copper foil, and a copper-clad laminate obtained from the adhesive. Board and printed circuit board, and multilayer circuit board and manufacturing method thereof, the polyimide-based adhesive is a composition formed by using the aforementioned polyimide, and an adhesive layer can be obtained, the adhesive layer is adhesive, heat-resistant Good adhesion, flow control and low dielectric properties.

As a result of intensive research, the present inventors found that a specific polyimide using a diamine component as a raw material exhibits a high storage stiffness modulus even under the temperature conditions of the B stage, and the diamine component not only contains As a diamine component, dimer diamine further contains trimer triamine in a specific amount. Furthermore, it was also found that by using the polyimide, an adhesive and a film-like adhesive which solve the aforementioned problems can be obtained.

That is, the present invention relates to a polyimide, a polyimide-based adhesive, a film-like adhesive material, an adhesive layer, an adhesive sheet, a copper-clad laminate, a printed wiring board, a multi-layer wiring board, and the manufacture thereof shown below. method.

(Item 1)

A polyimide (1) is a reactant comprising a monomer group of an aromatic tetracarboxylic anhydride (A) and a diamine (B), wherein the diamine (B) is in a mass ratio (b1)/( b2) dimer diamine (b1) and trimer triamine (b2) are contained so that it may become in the range of 97/3-70/30.

(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 =1-20.

(Item 3)

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。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 above items 1 to 3, wherein the monomer group further comprises a diamine polysiloxane (b3). (Item 5) The polyimide (1) according to the above 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-mentioned item 4 or 5, wherein the components (b1) and (b2), and the components (b1), (b2) and (b3), are mixed with each other. The ear ratio is 0.3<[[(b1)+(b2)]/[(b1)+(b2)+(b3)]]<1. (Item 7) A polyimide-based adhesive comprising the polyimide (1) described in any one of the above items, a crosslinking agent (2), and an organic solvent (3). (Item 8) The polyimide-based adhesive according to the above-mentioned item 7, wherein the crosslinking agent (2) is selected from epoxy compounds, benzoxazine compounds, bismaleimide compounds and cyanogens At least one of the group consisting of acid ester compounds. (Item 9) The polyimide-based adhesive according to the above-mentioned item 8, wherein the epoxy compound is a tetraglycidyldiamine of the following structure:

In the above formula, Y represents a phenylene group or a cyclohexylene group. (Item 10) The polyimide-based adhesive according to any one of the above 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 component (3) is 150 to 900 parts by mass. (Item 11) A film-like adhesive material obtained from the polyimide-based adhesive described in any one of the above items 7 to 9. (Item 12) An adhesive layer obtained from the polyimide-based adhesive described in any one of the above items 7 to 10 or the film-like adhesive material described in the above item 11. (Item 13) An adhesive sheet comprising the adhesive layer described in the above item 12 and a support film. (Item 14) A resin-attached copper foil, comprising the adhesive layer described in the above-mentioned item 12 and the copper foil. (Item 15) A copper-clad laminate comprising the resin-attached copper foil described in the above-mentioned item 14 and a copper foil. (Item 16) A copper clad laminate comprising the resin-attached copper foil described in the above item 15 and an insulating sheet. (Item 17) A printed wiring board obtained by forming a circuit pattern on the copper foil surface of the copper-clad laminate described in the above item 15 or 16. (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 base materials that are a printed circuit board or a printed circuit board . (Item 19) A method for manufacturing a multilayer wiring board, comprising the following steps 1 and 2: Step 1, by making the polyimide-based adhesive described in any one of the above items 7 to 10 or the above The film-like adhesive material described in item 11 is in contact with the core material, that is, a printed circuit board or at least one side of a printed circuit board, to manufacture a substrate with an adhesive layer; On the base material of the adhesive layer, a printed circuit board or a printed circuit board is laminated, and the steps of lamination are carried out under heating and pressure.

The polyimide (1) of the present invention exhibits a high storage stiffness modulus even under the temperature conditions of the B stage. Therefore, the adhesive obtained by using the polyimide, and the film-like adhesive material obtained from the adhesive are less likely to bleed or flow out of the adhesive in the B stage, and have heat-resistant adhesion and low dielectric properties. Good, so it is especially suitable for high frequency printed wiring board applications. The high-frequency printed circuit board manufactured by using the adhesive and the adhesive material has less transmission loss of high-frequency electrical signals, so it is suitable for mobile communication equipment or its bases represented by smart phones or mobile phones. Devices, servers/routers and other network-related electronic devices, mainframe computers, etc.

The polyimide (1) (hereinafter referred to as component (1)) of the present invention is a polymer containing aromatic tetracarboxylic anhydride (A) (hereinafter referred to as component (A)) and diamine (B) (hereinafter referred to as component (B)) as a reaction component, the diamine (B) contains a dimer diamine ( b1) (hereinafter referred to as component (b1)) and trimer triamine (b2) (hereinafter referred to as component (b2)).

As a component (A), various well-known aromatic tetracarboxylic anhydrides can be used. Specifically, aromatic tetracarboxylic anhydrides represented by the following structures can be used.

(上述式中，X表示單鍵、-SO₂-、-CO-、-O-、-O-C₆H₄-C(CH₃)₂-C₆H₄-O-或-COO-X¹-OCO-(X¹表示-(CH₂) _l -(l=1~20)或-H₂C-HC(-O-C(=O)-CH₃)-CH₂-)。)

(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 pyromellitic dianhydride, 4,4'-oxybis(phthalic anhydride), 3,3',4,4'-diphenyl ketone tetra Formic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-diphenyltetracarboxylic 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'-diphenylketone tetracarboxylic dianhydride , 2,3,3',4'-diphenyl ether tetracarboxylic dianhydride, 2,3,3',4'-diphenyl tetracarboxylic dianhydride, 2,2-bis(3,3', 4,4'-Tetracarboxyphenyl)tetrafluoropropane dianhydride, 2,2'-bis(3,4-dicarboxyphenoxyphenyl)stilbene dianhydride, 2,2-bis(2,3-dicarbonate) Carboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, and 4,4'-[propane-2,2-diylbis(1,4-phenylene) oxy)] 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), the normal temperature adhesiveness, the heat-resistant adhesiveness, etc., it is preferably at least one selected from the group consisting of: 3, 3',4,4'-Diphenylketonetetracarboxylic dianhydride, 4,4'-[Propan-2,2-diylbis(1,4-phenyleneoxy)]bis(phthalate) acid anhydride), and 4,4'-oxybis(phthalic anhydride).

Component (b1) is obtained by substituting all carboxyl groups of unsaturated fatty acids such as oleic acid, that is, all carboxyl groups of dimer acid, into primary amine groups (refer to Japanese Patent Laid-Open No. 9-12712, etc.), and can be used without special Various well-known ingredients are used with limitations. 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 the dotted line part means a carbon-carbon single bond or a carbon-carbon double bond).

Examples of commercially available products of the component (b1) include Versamine 551 (manufactured by BASF, Japan), Versamine 552 (manufactured by Corning Co., Ltd., a hydride of Versamine 551), PRIAMINE 1075, and PRIAMINE 1074 (all from Japan). Manufactured by Koluoda Co., Ltd.), etc. In addition, the dimer diamine component in these commercially available products is generally about 95 to 98% by mass, and the remainder may contain trimer triamine described later, and it is generally in the range of 2% by mass or less. .

Component (b2) is obtained by substituting all carboxyl groups of unsaturated fatty acids such as oleic acid, that is, trimer acid (refer to JP 2013-505345 Gazette, etc.) to primary amine groups, and can be obtained without special Various well-known ingredients are used with limitations. The following shows the non-limiting structural formula of trimer triamine (in each structural formula, m+n=6～17, p+q=8～19, and the dotted line part means carbon-carbon single bond or carbon-carbon double bond, R Means ethylidene ( _-CH2CH2- ) or vinylidene (-CH= _CH- )).

As a commercial item of a component (b1), PRIAMINE 1071 (made by Nippon Koloda Co., Ltd.) etc. are mentioned. In addition, the trimer triamine component in these commercial items is generally about 15 to 20 mass %, and the remainder may contain the aforementioned dimer diamine in excess of 80 mass %.

The mass ratio [(b1)/(b2)] of the component (b1) and the component (b2) in the component (B) is about 97/3 to 70/30. By being within the above-mentioned range, the balance between the flow controllability and the heat-resistant adhesiveness can be improved. From this viewpoint, the ratio is preferably about 96/4 to 75/25, more preferably about 95/5 to 75/25, further preferably about 93/7 to 75/25, and most preferably about 93/7 ~83/17 or so.

The preparation method of the component (B) is not particularly limited. For example, a method of mixing the above-mentioned component (b1) and component (b2) produced by various well-known methods so as to achieve the above-mentioned mass ratio, or mixing the above-mentioned so as to achieve the above-mentioned molar ratio can be exemplified. The commercially available product of the component (b1) was mixed with the commercially available product of the aforementioned component (b2).

The molar ratio of the component (A) to the component (B) is not particularly limited, but is generally 1<[(A)/(B from the viewpoint of maintaining a high storage stiffness modulus at a high temperature. )]<1.5, in general, preferably 1.03≦[(A)/(B)]≦1.4, and more preferably 1.07≦[(A)/ (B)]≦1.4, preferably 1.09≦[(A)/(B)]≦1.16.

In the present invention, a diamine polysiloxane (hereinafter referred to as a component (b3)) may be contained in the monomer group containing the component (A) and the component (B). Examples of the component (b3) include 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. Examples of components (B) other than (b1) to (b3) include diaminocyclohexane, diaminodicyclohexylmethane, dimethyl-diaminodicyclohexylmethane, diaminocyclohexylmethane, 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[4-(3-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, etc. bis(aminophenoxyphenyl) ) propanes; 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether and other diaminodiphenyl ethers Phenylenediamines such as p-phenylenediamine and m-phenylenediamine; 3,3'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4'- Diaminodiphenyl sulfides such as diaminodiphenyl sulfide; 3,3'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4'- Diaminodiphenyl benzene and other diamino diphenyl ketones; 3,3'-diamino diphenyl ketone, 4,4'-diamino diphenyl ketone, 3,4'-diamine Diaminodiphenyl ketones such as diaminodiphenyl ketone; 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane Diaminodiphenylmethanes such as phenylmethane; 2,2-bis(3-aminophenyl)propane, 2,2-bis(4-aminophenyl)propane, 2-(3-aminophenyl)propane Phenyl)-2-(4-aminophenyl)propane and other bis(aminophenyl)propanes; 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 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)- Bis(aminophenyl)phenylethanes such as 1-phenylethane; 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)benzenes; 1,3-bis (3-aminobenzyl)benzene, 1,3-bis(4-aminobenzyl)benzene, 1,4-bis(3-aminobenzyl)benzene, 1,4- Bis(aminobenzyl)benzenes such as bis(4-aminobenzyl)benzene; 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-alpha) , α-dimethylbenzyl)benzene and other bis(aminodimethyl)benzenes; 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, bis(aminobis(trifluoromethyl)benzyl) such as 1,4-bis(4-amino-α,α-bis(trifluoromethyl)benzyl)benzene Benzenes; 2,6-bis(3-aminophenoxy)benzonitrile, 4,4'-bis(3-aminophenoxy)biphenyl, 4,4'-bis(4-aminophenoxy) Phenoxy) biphenyl and other aminophenoxy biphenyls; bis[4-(3-aminophenoxy)phenyl]ketone, bis[4-(4-aminophenoxy)phenyl] Ketones and other aminophenoxyphenyl ketones; bis[4-(3-aminophenoxy)phenyl]sulfide, bis[4-(4-aminophenoxy)phenyl]sulfide, etc. Aminophenoxyphenyl sulfides; bis[4-(3-aminophenoxy)phenyl] bis[4-(4-aminophenoxy)phenyl] bis[4-(4-aminophenoxy)phenyl] benzene and other aminobenzenes Oxyphenyls; bis[4-(3-aminophenoxy)phenyl]ether, bis[4-(4-aminophenoxy)phenyl]ether and other aminophenoxyphenyls Ethers; 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 2,2-bis[3-(3-aminophenoxy)phenyl]-1,1, Amines such as 1,3,3,3-hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane Benzylphenoxyphenylpropanes; Examples of components (B) other than (b1) to (b3) other than the above include: 1,3-bis[4-(3-aminophenoxy) base)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, 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-dimethylbenzene Methyl]benzene, 4,4'-bis[4-(4-aminophenoxy)benzyl]diphenyl ether, 4,4'-bis[4-(4-amino-α, α-Dimethylbenzyl)phenoxy]diphenyl ketone, 4,4'-bis[4-(4-amino-α,α-dimethylbenzyl)phenoxy]diphenyl Base, 4,4'-bis[4-(4-aminophenoxy)phenoxy]diphenyl, 3,3'-diamino-4,4'-diphenoxydiphenyl base ketone, 3,3'-diamino-4,4'-dibenzyloxydiphenyl ketone, 3,3'-diamino-4-phenoxydiphenyl ketone, 3,3' -Diamino-4-biphenoxydiphenyl ketone, 6,6'-bis(3-aminophenoxy)-3, 3,3',3'-Tetramethyl-1,1'-spirobisindan, 6,6'-bis(4-aminophenoxy)-3,3,3',3'-tetramethyl Base-1,1'-spirobisindan, bis(aminomethyl)ether, bis(2-aminoethyl)ether, bis(3-aminopropyl)ether, bis[(2-amino Methoxy)ethyl]ether, bis[2-(2-aminoethoxy)ethyl]ether, bis[2-(3-aminopropoxy)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-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 2,6-bis(3-aminophenoxy)pyridine, etc. Two or more of these components may be combined.

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

The usage ratios of (b1) to (b3) are not particularly limited. Generally speaking, the molar ratio of the components (b1) and (b2) to the components (b1), (b2) and (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, if necessary, the component (b3) are mixed The component (B) undergoes a polymerization addition reaction for about 0.1 to 2 hours (preferably about 0.1 to 0.5 hours). Then, further at a temperature of about 80 to 250 ° C, preferably 100 to 200 ° C, the obtained polymer adduct is subjected to an imidization reaction, that is, a dehydration ring-closure reaction for about 0.5 to 50 hours (preferably 1 to 50 hours). about 20 hours), whereby the target component (1) can be obtained.

In addition, in the imidization reaction, various well-known reaction catalysts, dehydrating agents, and organic solvents described later can be used. 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, etc. ; and two or more of these reaction catalysts can be combined. Moreover, as a dehydrating agent, for example, aliphatic acid anhydrides, such as acetic anhydride, aromatic acid anhydrides, such as benzoic anhydride, etc. are mentioned, and 2 or more types of these dehydrating agents can be combined.

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

The physical properties of the component (1) obtained in this way are not particularly limited, and examples of the upper limit of the glass transition temperature include 250, 200, 150, and 100° C., and examples of the lower limit include 90 and 80 , 70, 60, 50, 40, 30, 20℃, etc. The range of the glass transition temperature can be appropriately set by selecting from the above-mentioned upper limit value and lower limit value, etc. From the viewpoint of the balance between normal temperature adhesion, heat resistance adhesion and low dielectric properties, the glass transition temperature is generally About 20-250 degreeC, Preferably it is about 30-200 degreeC. In addition, the weight average molecular weight is not particularly limited either, and examples of the upper limit include 60,000, 50,000, 40,000, 30,000, 20,000, 10,000, 9,000, 8,000, 7,000, 6,000, 5,000, and the like; and examples of the lower limit include : 50000, 40000, 30000, 20000, 10000, 9000, 8000, 7000, 6000, 5000, 4000, 3000, etc. For example, the range of the weight average molecular weight can be appropriately set by selecting from the above-mentioned upper limit value and lower limit value, etc. From the same viewpoint as above, it is generally about 3,000 to 60,000, preferably about 6,000 to 40,000. For example, the weight average molecular weight can be determined as a value in terms of polystyrene obtained by measurement by colloidal permeation chromatography (GPC).

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

As the component (2), various known components can be used without particular limitation as long as they can exhibit performance as a crosslinking agent of polyimide. Specifically, for example, at least one selected from the group consisting of epoxy compounds, benzoxazine compounds, bismaleimide compounds, and cyanate ester compounds is preferred.

As said epoxy compound, a phenol novolak type epoxy compound, a cresol novolak type epoxy compound, a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, a bisphenol S type epoxy compound are mentioned, for example: , Hydrogenated bisphenol A type epoxy compound, hydrogenated bisphenol F type epoxy compound, diphenylvinyl type epoxy compound, epoxy compound containing triazine skeleton, epoxy compound containing perylene skeleton, linear aliphatic ring Oxygen compound, alicyclic epoxy compound, glycidylamine type epoxy compound, trisphenolmethane type epoxy compound, alkyl modified trisphenolmethane type epoxy compound, biphenyl type epoxy compound, containing dicyclopentane Diene skeleton epoxy compounds, naphthalene skeleton-containing epoxy compounds, arylalkylene-type epoxy compounds, tetraglycidyl xylene diamine, modified epoxy compounds obtained by modifying these epoxy compounds with dimer acid quality epoxy compound, dimer acid diglycidyl ester, etc.; and two or more kinds can be combined. In addition, examples of commercially available products 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 Nippon Steel 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 bisphenol A-type epoxy compounds, bisphenol A-type epoxy compounds, bisphenol A-type epoxy compounds, Phenol F type epoxy compound, hydrogenated bisphenol A type epoxy compound, and alicyclic epoxy compound.

(式中，Y表示伸苯基或伸環己基)In particular, the tetraglycidyldiamine having the following structure has good compatibility with the component (1). Moreover, when this tetraglycidyl xylene diamine is used, the low-loss elastic modulus of the adhesive layer can be easily obtained, and the heat-resistant adhesive properties and low-dielectric properties can also be improved.

(wherein, Y represents phenylene or cyclohexylene)

When an epoxy compound is used as the component (2), various known curing agents for epoxy compounds can be used in combination. Specifically, for example: succinic anhydride, phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, 3-methyl-hexahydrophthalic anhydride Formic anhydride, 4-methyl-hexahydrophthalic anhydride, or a mixture of 4-methyl-hexahydrophthalic anhydride and hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyl - Tetrahydrophthalic anhydride, nadic anhydride, methyl nadic anhydride, norbornane-2,3-dicarboxylic anhydride, methylnorbornane-2,3-dicarboxylic anhydride, methyl Acid anhydride-based hardeners such as cyclohexenedicarboxylic anhydride, 3-dodecenyl succinic anhydride, and octenyl succinic anhydride; dicyandiamine (DICY), aromatic diamines (trade names "LonzacureM-DEA", " Lonzacure M-DETDA" etc. All are manufactured by Lonza Japan Ltd.), aliphatic amines and other amine hardeners; phenol novolac resin, cresol novolak resin, bisphenol A novolak resin, triazine modified phenol novolak resin Resins, phenolic hardeners such as phosphazene containing a phenolic hydroxyl group (trade name "SPH-100" manufactured by Otsuka Chemical Co., Ltd., etc.), cyclic phosphazene-based compounds; maleic acid-modified rosin or its hydrogenation rosin-based crosslinking agents, etc., etc.; and two or more kinds can be combined. Among them, a phenol-based hardener is preferable, and a phenolic hydroxyl group-containing phosphazene-based hardener is particularly preferable. The usage-amount of these hardeners is not particularly limited, but 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 can be used. Specifically, for example: 1,8-diaza-bicyclo[5.4.0]undec-7-ene, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylamine tertiary amines such as ethanol, ginseng (dimethylaminomethyl)phenol; 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole Isimidazoles; tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, phenylphosphine and other organic phosphines; tetraphenyl phosphonium tetraphenylborate, tetraphenyl phosphine Tetraphenylborates such as 2-ethyl-4-methylimidazole boronic acid, N-methylmorpholine tetraphenylboronic acid, etc.; and two or more kinds can be combined. In addition, the usage-amount of this reaction catalyst is not specifically limited, Generally, it is about 0.01-5 mass % when the solid content of the adhesive of this invention is 100 mass %.

As said benzoxazine compound, 6,6-(1-methylethylene)bis(3,4-dihydro-3-phenyl-2H-1,3-benzoxazine) is mentioned, for example. , 6,6-(1-methylethylene)bis(3,4-dihydro-3-methyl-2H-1,3-benzoxazine), etc.; and two or more kinds may be combined. In addition, a phenyl group, a methyl group, a cyclohexyl group, etc. may be bonded to the nitrogen of the oxazine ring. Moreover, as a commercial item, "Benzoxazine F-a type" or "Benzoxazine P-d type" made by Shikoku Chemical Industry Co., Ltd., "RLV-100" made by AIR WATER, etc. are mentioned, for example.

Examples of the bismaleimide compound include 4,4'-diphenylmethane bismaleimide, m-phenylene bismaleimide, and bisphenol A diphenyl ether bismaleimide. Leylimide, 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'-diphenyl bismaleimide, etc.; and two or more kinds can be combined. Moreover, as a commercial item, "BAF-BMI" by JFE Chemical Co., Ltd. etc. is mentioned, for example.

As said cyanate ester compound, 2-allylphenol cyanate, 4-methoxyphenol cyanate, 2,2-bis(4-cyanatophenol)-1,1,1 are mentioned, for example. ,3,3,3-hexafluoropropane, bisphenol A cyanate, diallyl bisphenol A cyanate, 4-phenylphenol cyanate, 1,1,1-sam(4-cyanic acid) phenyl)ethane, 4-cumylphenylphenol cyanate, 1,1-bis(4-cyanatophenyl)ethane, 4,4'-bisphenol cyanate, and 2,2 -bis(4-cyanatophenyl)propane, etc.; and two or more kinds may be combined. Moreover, as a commercial item, "PRIMASET BTP-6020S (made by Nippon Lonza 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, dimethylsulfoxide, N-methylcaprolactamide, methyltrisamine Aprotic polar solutions such as glyme and methyl diglyme; or alicyclic solvents such as cyclohexanone and methylcyclohexane; methanol, ethanol, propanol, benzyl alcohol, cresol Alcohol-based solvents such as toluene; aromatic solvents such as toluene; and two or more of these organic solvents can be combined. Moreover, the usage-amount of this organic solvent is not specifically limited, Generally, it is in the range of about 10-60 mass % of the solid content mass of the resin composition of this invention.

The usage-amount of the component (1), the component (2), and the component (3) in the polyimide-based adhesive of the present invention is not particularly limited, but is calculated in terms of solid content with respect to 100 parts by mass of the component (1) , as an example of the upper limit of the component (2), 60, 50, 40, 30, 20, 10 parts by mass, etc.; as an example of a lower limit, 50, 40, 30, 20, 10, 5, 3 , 2 parts by mass, etc.; as examples of the upper limit of the 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, etc. For example, the range of the above-mentioned component (2) and component (3) can be selected from the above-mentioned upper limit value and lower limit value, etc., and the range of the above-mentioned component (2) and component (3) can be selected from the handling properties at the time of coating, heat resistance, electrical properties, adhesiveness, etc. as the adhesive From the viewpoint of the balance of physical properties, in general, 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 component ( 3) It is about 150-900 mass parts, Preferably it is about 200-500 mass parts.

The polyimide-based adhesive of the present invention is obtained, for example, by a method of dissolving the component (1) and the component (2) in the component (3). In addition, the aforementioned ring-opening esterification catalyst or dehydrating agent, plasticizer, weathering agent, antioxidant, heat stabilizer, lubricant, antistatic agent, whitening agent, colorant, and conductive agent may be blended as required. , mold release agent, surface treatment agent, viscosity modifier, phosphorus flame retardant, flame retardant filler, silica filler, and fluorine filler 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, for example, it is obtained by applying the adhesive to a suitable support, heating the component (3) to volatilize, and curing it, and then peeling it off from the support. The thickness of the adhesive material is not particularly limited, but is generally about 3 to 40 μm. As this support body, the following support body is mentioned.

The adhesive sheet of the present invention is an article comprising as its constituent elements: an adhesive layer obtained from the polyimide-based adhesive of the present invention or the film-like adhesive material of the present invention; and a support film. Examples of the support include the following plastic films: polyester, polyimide, polyimide-silicon dioxide blend, polyethylene, polypropylene, polyethylene terephthalate, polyethylene naphthalate Ethylene formate, polymethyl methacrylate resin, polystyrene resin, polycarbonate resin, acrylonitrile-butadiene-styrene resin, ethylene terephthalate, or by phenol, phthalic acid , hydroxynaphthoic acid, etc., and aromatic polyester resin obtained from p-hydroxybenzoic acid (so-called liquid crystal polymer, "Vecstar" manufactured by Kuraray Co., Ltd., etc.) and the like. Moreover, when apply|coating the polyimide-type adhesive of this invention on this support body, the said application|coating means can be used. The thickness of the coating layer is also not particularly limited, but generally, the thickness after drying may be within a range of about 1 to 100 μm, preferably within a range of about 3 to 50 μm. In addition, the adhesive layer of the adhesive sheet can be protected by a protective film.

The resin-attached copper foil of the present invention is an article including, as its constituent elements, the adhesive layer of the present invention and the copper foil. Specifically, it is an article obtained by coating or sticking the polyimide-based adhesive or the film-like adhesive material on a copper foil. As this copper foil, a rolled copper foil or an electrolytic copper foil is mentioned, for example. The thickness is not particularly limited, but is generally about 1 to 100 μm, preferably about 2 to 38 μm. In addition, this copper foil may be a copper foil after various surface treatments (roughening, rust-proofing, etc.) are applied. Examples of the anti-rust treatment include plating treatment using a plating solution containing nickel, zinc, tin, or the like, or so-called mirror treatment such as chromate treatment. Moreover, as a coating means, the said method is mentioned. In addition, the adhesive layer of the resin-attached copper foil may not be hardened, and may be partially hardened or fully hardened by heating. The partially hardened adhesive layer is in a state called the so-called B-stage. In addition, the thickness of the adhesive layer is not particularly limited, but is generally about 0.5 to 3.0 μm. Moreover, copper foil can be further bonded to the adhesive surface of this resin-attached copper foil, and a double-sided resin-attached copper foil can be produced.

The copper clad laminate of the present invention is an article, which is formed by laminating the resin-attached copper foil and copper foil or insulating sheet of the present invention, and is also called copper clad laminate (CCL, copper clad laminate). . Specifically, it is an article obtained by pressing the resin-attached copper foil of the present invention to at least one or both surfaces of various known copper foils or insulating sheets under heating. When pasting on one of the surfaces, a different one from the resin-attached copper foil of the present invention can be pressed on the other surface. In addition, the number of sheets of the copper foil with resin and the insulating sheet in the copper-clad laminate is not particularly limited. Moreover, as this insulating sheet, a prepreg is preferable. 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 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 to 240°C) and about 0.5 to 20 MPa (preferably about 1 to 8 MPa).

The printed wiring board of the present invention is an article obtained by forming a circuit pattern on the copper foil surface of the copper-clad laminate of the present invention. As means of patterning, for example, a subtractive method or a semi-additive method can be mentioned. Examples of the semi-additive method include, for example, the following method: patterning with a resist film on the copper foil surface of the copper-clad laminate of the present invention, then performing electrolytic copper plating, removing the resist, and then adding an alkaline solution Etch. In addition, the thickness of the circuit pattern layer in this printed wiring board is not specifically limited. Moreover, 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 well-known printed wiring boards or printed wiring boards thereon. In addition to the polyimide-based adhesive of the present invention, other known polyimide-based adhesives may be used for lamination. In addition, the number of build-up layers in the multilayer substrate is not particularly limited. In addition, through-holes can be inserted for each build-up, 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. In addition, the height of the said circuit pattern is not specifically limited, either, Usually, it is about 1-50 micrometers.

The multilayer circuit board of the present invention is an article, and as its constituent elements, it includes: a core material, that is, a printed circuit board or a printed circuit board, the adhesive layer of the present invention, and other base materials, that is, a printed circuit board or a printed circuit board. A printed circuit board. Said printed circuit board or a printed circuit board can be the printed circuit board or printed circuit board of the present invention, and can 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 comprising the following steps 1 and 2. Step 1 is to make the polyimide-based adhesive or film-like adhesive material of the present invention in contact with the core material, that is, a printed circuit board or at least one side of a printed circuit board, to manufacture the adhesive layer attached. Substrate steps. Step 2 is a step of laminating a printed circuit board or a printed circuit board on the substrate with the adhesive layer, and laminating under heating and pressure.

Said printed circuit board or a printed circuit board can be the printed circuit board or printed circuit board of the present invention, and can also be a known printed circuit board or printed circuit board.

In step 1, the means for contacting the polyimide-based adhesive or the film-like adhesive material of the present invention with the adhesive is not particularly limited, and various known coating means can be used, such as a curtain coater, Roll coaters, laminators, presses, etc.

The heating temperature and the pressing time in step 2 are not particularly limited. Generally speaking, it is preferable that (a) at least one of the polyimide-based adhesives or film-like adhesive materials of the present invention and the core material be used. After contacting with one side, it is generally first heated to about 70 to 200° C., and takes about 1 to 10 minutes to carry out a hardening reaction, (b) and then further heat treatment is performed to advance the hardening reaction of the component (2). The conditions are generally about 150 ℃ ~ 250 ℃, about 10 minutes to 3 hours. In addition, the pressure is not particularly limited, but in the entire steps (a) and (b), it is generally about 0.5 to 20 MPa, preferably about 1 to 8 MPa. [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 addition, in each example, unless otherwise specified, parts and % are based on mass.

<Production of polyimide> (Production Example 1) 300.00 g of 4,4'-[propane-2,2-diylbis( 1,4-phenyleneoxy)]bis(phthalic anhydride) (trade name "BisDA-1000", manufactured by SABIC Innovative Plastics Japan LLC., hereinafter referred to as "BisDA-1000") BisDA), 1042.73 g of cyclohexanone, and 208.55 g of methylcyclohexane, and heated to 60°C. Then, 289.36 g of commercially available trimer triamine (trade name "PRIAMINE 1071", trimer triamine/dimer diamine mass ratio = 20/80, manufactured by Nippon Coloda Co., Ltd.) was added dropwise. , and the imidization reaction was performed at 140° C. for 12 hours to obtain a solution of polyimide (1-1) (nonvolatile content: 31.9%). In addition, the molar ratio of the acid component/amine component of this polyimide was 1.13.

In the production examples and comparative production examples other than Production Example 1, the composition of the resin solution was changed as described in Table 1, and the same procedure as in Production Example 1 was performed to obtain polyimide. For example, Comparative Production Example 1 was carried out 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 commercially available dimer diamine (trade name "PRIAMINE 1075", trimer triamine/dimer diamine mass ratio = 2/98, manufactured by Japan Koloda Co., Ltd.) was gradually added. ), the polyimide (2-1) (nonvolatile content 35.7%) was obtained by heating to 140° C. and implementing imidization reaction over 12 hours. In addition, the molar ratio of the acid component/amine component of this polyimide was 1.05.

[Table 1] BisDA-1000‧‧‧4,4'-[Propane-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 Koloda Co., Ltd. PRIAMINE1075‧‧‧trimer triamine/dimer diamine mass ratio = 2/98, manufactured by Japan Koluoda Co., Ltd.

<Measurement of storage rigidity modulus> The solutions of Production Example 1 and Comparative Production Example 1 were coated on NAFLON PTFE tape No. 9001 (manufactured by Nigas Co., Ltd.), dried at room temperature for 12 hours, and then It dried under the conditions of 150 degreeC and 5 minutes, and produced the adhesive sheet of about 20 micrometers.

Next, the adhesive sheet was folded to prepare a sheet having a thickness of about 300 μm, and 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 stiffness modulus. sex. In addition, the temperature increase rate was 10 degreeC/min. The results are shown in FIG. 1 .

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

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 was carried out according to the following procedure.

(Comparative Example 1) 100.00 g of a solution of polyimide resin (2-1) and 0.73 g of bisphenol A-type epoxy resin (manufactured by Nippon Epoxy Resin Co., Ltd., trade name) as component (2) were mixed "jER828", epoxy equivalent 190g/eq), 3.24g of hydroxyl-containing polyphenylene ether (trade name "SA90", manufactured by SABIC Innovative Plastics Japan Co., Ltd., hydroxyl equivalent 840g/eq), and as an organic solvent 28.24 g of toluene was uniformly stirred to obtain a resin composition with a nonvolatile content of 30.0%.

[Table 2] In addition, the organic solvent used when manufacturing polyimide may be contained in the organic solvent (3). SG-708-6: Acrylic elastomer manufactured by Nagase ChemteX Corporation.

<Preparation of an adhesive sheet> The adhesive composition of Example 1 was applied to the block copolymerized polyimide-oxide using a gap coater so that the thickness after drying was 20 μm and each of the left and right edges was 1 cm. Silicon blend film (trade name "POMIRAN N25", manufactured by Arakawa Chemical Industry Co., Ltd., thermal expansion coefficient = 18ppm, tensile modulus = 5.9GPa, film thickness 25μm, width 10cm, length 15cm), then dried at 180°C for 3 minutes, thereby obtaining an adhesive sheet.

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

Next, the test sample was placed on a support for pressurization, and a support body obtained from the same material was interposed therebetween, and heated and pressurized from above under the conditions of a pressure of 5 MPa, 170° C. and 30 minutes, thereby producing a laminate. film.

1. Adhesion test According to Japanese Industrial Standard (JIS) C 6481 (Test method for copper clad laminates for flexible printed wiring boards), the peel strength (N/cm) of the aforementioned copper clad laminates was measured. 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 so that the copper foil side was downward, and the appearance change was checked. No change was made into ○, and the case with foaming and swelling was made into x. The results are shown in Table 3.

3. Evaluation of flow controllability After visually inspecting the right end of the adhesive layer (hardened layer) in the above-mentioned laminated film, it was confirmed that the position of the rear end did not change before and after heating and pressing. That is, even if this hardened layer was heated and pressurized, it did not flow out (0 mm) in the horizontal direction, and it was found that the flow controllability was good. The results are shown in Table 3.

<Preparation of hardened product sample for dielectric constant measurement> About 7 g of the adhesive composition of Example 1 was poured into a fluororesin PFA flat plate (75 mm in diameter, manufactured by Mutual Chemical Glass Co., Ltd.), and heated at 30°C for 10 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, to obtain a cured product sample with a film thickness of about 300 μm for dielectric constant measurement.

Then, in accordance with JIS C2565, the dielectric constant and dielectric loss tangent at 10 GHz of the cured product sample were measured using a commercially available dielectric constant measuring device (cavity resonator type, manufactured by AET Corporation). The results are shown in Table 3.

Also about the adhesive composition of the comparative example 1, it carried out in the same manner, and implemented the test 1-3. In Test 3, it was confirmed that the hardened layer flowed out in a gentle wave-like manner about 2 mm in the horizontal direction of POMIRAN N25 in the laminated film for this test.

[table 3]

1‧‧‧Insulating film 2‧‧‧Adhesive layer 3‧‧‧Copper foil

FIG. 1 is a graph showing the temperature change of the storage stiffness modulus of the polyimide (1-1) of Production Example 1 and the polyimide (1-2) of Comparative Example 1. Fig. 2 is a schematic diagram of a sample for a flow control test; further, in Fig. 2, symbol 1 denotes an insulating film (block copolymerized polyimide-silicon oxide hybrid film), symbol 2 denotes an adhesive layer of the present invention, Reference numeral 3 represents copper foil.

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

(Please change the page and record it separately) None

Claims (21)

A polyimide (1) is a reactant comprising a monomer group of an aromatic tetracarboxylic anhydride (A) and a diamine (B), wherein the diamine (B) comprises a mass ratio (b1)/ (b2) is dimer diamine (b1) and trimer triamine (b2) in the range of 97/3~70/30, and the molar ratio of component (A) to component (B) is 1<[ (A)/(B)]<1.5. 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 -, wherein l =1~20 or X ¹ represents -H ₂ C-HC(-OC(=O)-CH ₃ )-CH ₂ -. The polyimide (1) according to claim 1 or 2, wherein the monomer group further comprises a diamine polysiloxane (b3). The polyimide (1) according to claim 1 or 2, 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 3, 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 3, wherein the component (b1), the component (b2), and the component (b1), the component (b2), and the component (b3) The molar ratio of is 0.3<[[(b1)+(b2)]/[(b1)+(b2)+(b3)]]<1. The polyimide (1) according to claim 4, 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. The polyimide (1) according to claim 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 comprising the polyimide (1) according to any one of claims 1 to 8, a crosslinking agent (2) and an organic solvent (3). The polyimide-based adhesive according to claim 9, wherein the crosslinking agent (2) is selected from the group consisting of epoxy compounds, benzoxazine compounds, bismaleimide compounds and cyanate ester compounds at least one of the group consisting of. The polyimide-based adhesive according to claim 10, wherein the epoxy compound is tetraglycidyldiamine of the following structure:

In the above formula, Y represents a phenylene group or a cyclohexylene group. The polyimide-based adhesive according to any one of claims 9 to 11, wherein the component (2) is 11 to 900 parts by mass in terms of solid content with respect to 100 parts by mass of the component (1), And component (3) is 150-900 mass parts. A film-like adhesive material obtained from the polyimide-based adhesive described in any one of claims 9 to 11. An adhesive layer obtained from the polyimide-based adhesive described in any one of claims 9 to 11 or the film-like adhesive material described in claim 13. An adhesive sheet, comprising the adhesive layer described in claim 14 and a support film. A resin-attached copper foil, comprising the adhesive layer and the copper foil as claimed in claim 14. A copper-clad laminate, comprising the resin-attached copper foil and a copper foil as claimed in claim 16. A copper-clad laminate, comprising the resin-attached copper foil as claimed in claim 16 and an insulating sheet. A printed wiring board formed by forming a circuit pattern on the copper foil surface of the copper-clad laminate according to claim 17 or 18. A multi-layer circuit board, comprising: a core material, namely a printed circuit board or a printed circuit board, the adhesive layer described in claim 14, and other base materials, namely a printed circuit board or a printed circuit board. A method for manufacturing a multilayer circuit board, comprising the following steps 1 and 2: Step 1, by making the polyimide-based adhesive described in any one of claim 9 to 11 or claim 13 The film-like adhesive material is in contact with the core material, that is, a printed circuit board or at least one side of a printed circuit board, to manufacture a base material with an adhesive layer; step 2 is to attach the base with the adhesive layer. On the material, a printed circuit board or a printed circuit board is laminated, and the step of pressing is carried out under heat and pressure.

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