TWI696680B - Polyimide-based adhesives, film-like adhesive materials, adhesive layers, adhesive sheets, copper-clad laminates and printed circuit boards, and multilayer circuit boards and methods of manufacturing the same - Google Patents

Abstract

The problem to be solved by the present invention is to provide a novel polyimide-based adhesive, which has a low loss elastic modulus at the B stage, and can obtain an adhesive layer with heat-resistant adhesiveness and low dielectric properties. Good electrical characteristics.

The solution of the present invention is a polyimide-based adhesive, which comprises: terminal modified polyimide (1), which is the reaction of acid anhydride group terminal polyimide (A1) and primary monoamine (A2) The acid anhydride group terminal polyimide (A1) is a reactant of an aromatic tetracarboxylic anhydride (a1) and a monomer group (α) containing a dimer diamine (a2), and the primary monoamine ( A2) is represented by the general formula X ¹ -NH ₂ (where X represents a hydrocarbon group having 1 to 22 carbon atoms); a cross-linking agent (2); and, an organic solvent (3).

Description

Polyimide-based adhesive, film-shaped adhesive material, adhesive layer, thin adhesive Sheet, copper-clad laminate and printed circuit board, and multilayer circuit board and manufacturing method thereof

The invention relates to a polyimide-based adhesive, a film-like adhesive material, an adhesive layer, an adhesive sheet, a copper-clad laminate, a printed circuit board, a multilayer circuit board, and a method for manufacturing the multilayer circuit board. The polyimide Adhesives are particularly useful when manufacturing multi-layer circuit boards (MLB: Multi-Layer Board). The film-like adhesive material is composed of the adhesive, the adhesive layer is obtained from the adhesive and the film-like adhesive material, and the adhesive sheet Contains this adhesive layer.

Flexible printed circuit boards (FPWB: Flexible Printed Wiring Board) and printed circuit boards (PCB: Printed Circuit Board), and multi-layer circuit boards derived from these have been widely used in mobile phones or smart phones Network-related electronic equipment such as communication equipment or its base station devices, servers/routers, large computers, and other products.

In recent years, in these products, in order to transmit/process large-capacity messages at high speed, high-frequency electrical signals are used, but high-frequency signals It is very easy to attenuate, so the above-mentioned multilayer circuit board also requires a means to suppress the transmission loss as much as possible.

As a means of suppressing transmission loss in a multilayer wiring board, for example, when laminating a printed wiring board or a printed circuit board, a polyimide-based adhesive is used, which not only has excellent heat-resistant adhesiveness, but also has a dielectric Both the constant and the dielectric loss tangent have low characteristics (hereinafter also referred to as low dielectric characteristics) (see, for example, Patent Documents 1 to 3). In addition, polyimide-based adhesives are sometimes used as film-like adhesive materials.

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

The multi-layer circuit board in which a high-definition/high-density substrate is laminated and has high adhesive reliability can be obtained by, for example, the following method. That is, the following steps: (1) The polyimide-based adhesive or the polyimide-based film-like adhesive material is brought into contact with the adherend, that is, one side of the printed wiring board or printed circuit board, thereby manufacturing the attached The substrate with an adhesive layer; (2) heating the substrate with an adhesive layer at a temperature of about 100 to 200°C, thereby making the adhesive layer semi-hardened (so-called B-stage); (3) On the adhesive layer in the B stage, a printed wiring board or a printed circuit board is further laminated and pressed under heating.

In the aforementioned step (2), the adhesive layer of stage B is required to have a moderate fluidity. This is due to the following reason: by spreading the adhesive layer over The fine irregularities on the surface of the adherend come up to minimize the gap and prevent poor insulation. On the other hand, the adhesive layer is required to have good heat-resistant adhesiveness and low dielectric properties after post-curing.

The fluidity of the adhesive layer in stage B can be evaluated by the loss elastic modulus, and the lower the loss elastic modulus, the better the fluidity. As a means of reducing the loss elastic modulus, for example, the following methods can be considered: lowering the molecular weight of the main agent, that is, polyimide, or introducing an ether linkage or branched structure into the molecule. However, the adhesive layer containing such a main agent may flow out from the end of the multilayer wiring board in the aforementioned step (3), or the heat-resistant adhesiveness and low dielectric characteristics are insufficient.

[Prior Technical Literature] (Patent Literature)

Patent Literature 1: Japanese Patent Laid-Open No. 2009-299040

Patent Document 2: Japanese Patent Laid-Open No. 2014-045076

Patent Document 3: Japanese Patent Application Publication No. 2014-086591

The main problem of the present invention is to provide a novel polyimide-based adhesive, which has a low loss elastic modulus at the B stage, and can obtain an adhesive layer with heat-resistant adhesiveness and low dielectric properties good.

The main problem of the present invention is also to provide a novel polyimide-based film-like adhesive material, which has a low loss elastic modulus at the B stage, and can obtain an adhesive layer whose heat-resistant adhesiveness and low The dielectric properties are good.

The inventors concentrated on research and found that the aforementioned problems can be solved by an adhesive that uses terminal-modified polyimide as the base resin, and the terminal-modified polyimide is a primary monoamine and a specific anhydride The terminal acid anhydride group of the terminal polyimide is reacted to obtain.

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

1. A polyimide-based adhesive, comprising: terminal modified polyimide (1), which is a reactant of an acid anhydride group terminal polyimide (A1) and a primary monoamine (A2), the acid anhydride The group-terminal polyimide (A1) is a reactant of an aromatic tetracarboxylic anhydride (a1) and a monomer group (α) containing a dimer diamine (a2), and the primary monoamine (A2) is It is represented by the general formula X ¹ -NH ₂ (where X ¹ represents a hydrocarbon group having 1 to 22 carbon atoms); a cross-linking agent (2); and, an organic solvent (3).

上述式中，Y表示單鍵、-SO₂-、-CO-、-O-、-O-C₆H₄-C(CH₃)₂-C₆H₄-O-或-COO-Y¹-OCO-(Y¹表示-(CH₂)₁-(1=1~20)或-H₂C-HC(-O-C(=O)-CH₃)-CH₂-)。 2. The polyimide-based adhesive according to item 1, wherein the component (a1) is represented by the following general formula,

In the above formula, Y represents a single bond, -SO ₂ -, -CO-, -O-, -OC ₆ H ₄ -C(CH ₃ ) ₂ -C ₆ H ₄ -O- or -COO-Y ¹ -OCO -(Y ¹ means -(CH ₂ ) ₁ -(1=1~20) or -H ₂ C-HC(-OC(=O)-CH ₃ )-CH ₂ -).

3. The polyimide-based adhesive as described in the above item 1 or 2, wherein the molar ratio of the component (a1) to the component (a2) is 1<[(a1)/(a2)]< 1.2.

4. The polyimide-based adhesive according to any one of items 1 to 3, wherein the monomer group (α) further includes a diamine polysiloxane (a3).

5. The polyimide-based adhesive according to item 4 above, wherein the ratio of the total moles of the component (a1) to the component (a2) and the component (a3) is 1<[(a1) /[(A2)+(a3)]]<1.2.

6. The polyimide-based adhesive according to the above item 4 or 5, wherein the ratio of the total molar ratio of the component (a2) to the component (a2) and the component (a3) is 0.3<[( a2)/[(a2)+(a3)]]<1.

7. The polyimide-based adhesive according to any one of the aforementioned items 1 to 6, wherein the component (A2) is represented by the general formula X ² -NH ₂ (where X ² represents the carbon number 1 ~22 linear, branched or cyclic alkyl, or aromatic groups) to represent the primary monoamine.

8. The polyimide-based adhesive according to any one of the above items 1 to 7, wherein the amount of the component (A2) used relative to 1 mole of the terminal anhydride group of the component (A1) It is 0.8~1.2 mol.

化合物、雙馬來醯胺化合物及氰酸酯化合物。 9. The polyimide-based adhesive according to any one of items 1 to 8 above, wherein the component (2) contains at least one selected from the group consisting of: an epoxy compound, Benzo

Compounds, bismaleamide compounds and cyanate compounds.

上述式中，Z表示伸苯基或環己烯基。 10. The polyimide-based adhesive according to item 9 above, wherein the epoxy compound contains tetraglycidoxypropylxylenediamine of the following structure,

In the above formula, Z represents phenylene or cyclohexenyl.

11. The polyimide-based adhesive according to any one of items 1 to 10, wherein the component (2) is 11 with respect to 100 parts by weight of the component (1) (in terms of solid content). ~900 parts by weight, and the component (3) is 150~900 parts by weight.

12. A film-like adhesive material comprising the polyimide-based adhesive according to any one of items 1 to 11 above.

13. An adhesive layer comprising the polyimide-based adhesive according to any one of the above items 1 to 11 or the film-like adhesive material according to the above item 12.

14. An adhesive sheet as its constituent elements, comprising: the adhesive layer and the supporting film as described in item 13 above.

15. A copper foil with resin as its constituent elements, comprising: the adhesive layer and the copper foil as described in item 13 above.

16. A copper-clad laminate comprising, as its constituent elements, the copper foil with resin and a copper foil as described in item 15 above.

17. A copper-clad laminate, as its constituent elements, comprising: the copper foil with resin as described in item 15 above and an insulating sheet.

18. A printed wiring board formed by forming a circuit pattern on the copper foil surface of the copper-clad laminate according to item 16 or 17 above.

19. A multilayer circuit board, as its constituent elements, including: a core substrate that is a printed circuit board or a printed circuit board, the adhesive layer as described in item 13 above, and other substrates that is a printed circuit board Or a printed circuit board.

20. A method of manufacturing a multilayer wiring board, comprising the following steps 1 and 2: Step 1, by using the polyimide-based adhesive as described in any one of items 1 to 11 or as described above Item 12 The film-like adhesive material Material, contacting the core substrate, that is, at least one side of a printed wiring board or a printed circuit board, to manufacture a substrate with an adhesive layer; Step 2, on the substrate with an adhesive layer, Laminate a printed wiring board or a printed circuit board, and perform the pressing step under heating and pressure.

The polyimide-based adhesive of the present invention has a low loss elastic modulus at the B stage and can exhibit moderate fluidity, so that the adherend, that is, a printed wiring board and a printed circuit board, can be made good Moist.

The polyimide-based film-like adhesive material of the present invention also has a low loss elastic modulus at the B stage, and can exhibit moderate fluidity, so it can interact with the adherend, that is, printed wiring boards and printed circuit boards, etc. Good adhesion.

The adhesive layer of the present invention, obtained from the aforementioned polyimide-based adhesive or polyimide-based film-like adhesive material, can exhibit moderate fluidity at the B stage, and can exhibit good heat-resistant adhesiveness after post-curing And low dielectric properties. This adhesive layer is sometimes referred to as "adhesive layer" hereinafter.

The polyimide-based adhesive of the present invention and the polyimide-based film-like adhesive material, and the adhesive sheet obtained using these, copper foil with resin, copper-clad laminate and printed wiring board are used as low Materials for multilayer circuit boards with excellent electrical characteristics are useful. In addition, the components obtained using these are useful as components of the following products that process high-frequency signals: mobile communication devices represented by smartphones or mobile phones or their base station devices, servers/routers, etc. Network-related electronic equipment, large computers, etc.

Fig. 1 is a graph showing the transition of the loss elastic modulus (G") of the polyimide-based adhesives of Example 3 and Comparative Example 2.

The polyimide adhesive of the present invention is a composition comprising: modified polyimide (1) (hereinafter also referred to as component (1)), which is a primary monoamine (A2) (hereinafter also referred to as It is the component (A2)) to block the terminal acid anhydride group of the specific acid anhydride group terminal polyimide (A1) (hereinafter also referred to as component (A1)); crosslinking agent (2) (hereinafter also referred to as Component (2)); and, organic solvent (3) (hereinafter also referred to as component (3)).

Component (A1) is a group of monomers containing aromatic tetracarboxylic anhydride (a1) (hereinafter also referred to as component (a1)) and a dimer diamine (a2) (hereinafter also referred to as component (a2)) α) (hereinafter also referred to as component (α)) reactant.

As the component (a1), various well-known aromatic tetracarboxylic anhydrides can be used. Specifically, for example, an aromatic tetracarboxylic anhydride represented by the following structure may be mentioned.

(上述式中，Y表示單鍵、-SO₂-、-CO-、-O-、-O-C₆H₄-C(CH₃)₂-C₆H₄-O-或-COO-Y¹-OCO-(Y¹表示-(CH₂)₁-(1=1~20)或-H₂C-HC(-O-C(=O)-CH₃)-CH₂-。)

(In the above formula, Y represents a single bond, -SO ₂ -, -CO-, -O-, -OC ₆ H ₄ -C(CH ₃ ) ₂ -C ₆ H ₄ -O- or -COO-Y ^1- OCO-(Y ¹ means -(CH ₂ ) ₁ -(1=1~20) or -H ₂ C-HC(-OC(=O)-CH ₃ )-CH ₂ -.)

Specific types of the component (a1) include, for example, 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'-diphenyl ash 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'-diphenyl ketone tetracarboxylic dianhydride , 2,3,3',4'-diphenyl ether tetracarboxylic dianhydride, 2,3,3',4'-diphenyl ether tetracarboxylic dianhydride, 2,2-bis(3,3', 4,4'-tetracarboxyphenyl)tetrafluoropropane dianhydride, 2,2'-bis(3,4-dicarboxyphenoxyphenyl) anthracen dianhydride, 2,2-bis(2,3-di Carboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl) propane dianhydride, cyclopentane tetracarboxylic anhydride, butane-1,2,3,4-tetracarboxylic acid, 2, 3,5-tricarboxycyclopentylacetic anhydride, and 4,4'-[propan-2,2-diylbis(1,4-phenyleneoxy)]bis(phthalic acid Acid anhydride), etc.; and two or more kinds can be combined. Among them, from the viewpoint of the balance of heat-resistant adhesiveness and low dielectric properties, it is preferably at least one selected from the group consisting of 3,3',4,4'-diphenyl ketone tetra Formic dianhydride, 4,4'-[propan-2,2-diylbis(1,4-phenyleneoxy)] bis(phthalic anhydride), and 4,4'-oxybis(o Phthalic anhydride).

Component (a2), which is a dimer diamine, is a compound derived from a dimer of unsaturated fatty acid such as oleic acid, that is, a dimer acid (refer to Japanese Patent Laid-Open No. 9-12712, etc.), and may not In particular, various known dimer diamines are used.

The non-limiting structural formula of the component (a2) is shown below. In each structural formula, m+n=6~17, p+q=8~19, and the dotted line means carbon-carbon single bond or carbon-carbon double bond.

Examples of commercially available products of component (a2) include Versamine 551 (made by BASF Corporation of Japan), Versamine 552 (made by Cognis Japan Ltd., hydride of Versamine 551), PRIAMINE 1075, and PRIAMINE 1074 (both Croda Japan KK Manufacturing), etc.; and more than two types can be combined.

The amount of the component (a1) and the component (a2) used is not particularly limited. From the viewpoint of the balance of low-loss elastic modulus of the adhesive layer, heat-resistant adhesiveness, and low dielectric properties, generally, the component ( The ratio of mole of a1) to mole of component (a2) is about 1<[(a1)/(a2)]<1.2, preferably 1.05≦[(a1)/(a2)]≦ Just about 1.15. By making the ratio greater than 1, there is a tendency to make the heat-resistant adhesiveness of the adhesive layer good, and by making the ratio less than 1.2, there is a tendency that the adhesive layer can be elasticized with low loss, and It also makes its low dielectric properties good.

The component (α) may also contain diamine polysiloxane (a3) (hereinafter also referred to as (a3)). The component (a3) can reduce the loss elastic modulus of the adhesive layer, and can improve its heat-resistant adhesive property.

As the component (a3), various well-known diamine polysiloxanes can be used. Specifically, for example, α,ω-bis(2-aminoethyl)polydimethylsiloxane, α,ω-bis(3-aminopropyl)polydimethylsiloxane, 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, etc.; and 2 or more combinations.

The amount of component (a1), component (a2), and component (a3) used is not particularly limited, and from the viewpoint of the balance of low-loss elastic modulus of the adhesive layer, heat-resistant adhesiveness, and low dielectric properties, it is generally In particular, the ratio of moles of component (a1) to the total moles of component (a2) and component (a3) is about 1<[(a1)/[(a2)+(a3)]]<1.2 Preferably, it should be within a range of 1.05≦[(a1)/[(a2)+(a3)]]≦1.15. By making the ratio greater than 1, there is a tendency to make the heat-resistant adhesiveness of the adhesive layer good, and by making the ratio less than 1.2, there is a tendency that the adhesive layer can be elasticized with low loss, and It also makes its low dielectric properties good.

The use ratio of the component (a2) and the component (a3) is not particularly limited, and from the viewpoint of the balance of low-loss elastic modulus of the adhesive layer, heat-resistant adhesiveness, and low dielectric properties, generally, the component ( The ratio of the mole of a2) to the total mole of component (a2) and component (a3) is 0.3< [(a2)/[(a2)+(a3)]] The degree of <1 is preferably within a range of 0.5≦[(a2)/[(a2)+(a3)]]≦1. By making the ratio greater than 0.3, there is a tendency to make the heat-resistant adhesion of the adhesive layer good, and by making the ratio less than 1, there is a tendency that the adhesive layer can be elasticized with low loss, and It also makes its low dielectric properties good.

The component (α) may contain a diamine component (hereinafter also referred to as component (a4)) other than component (a2) and component (a3) as necessary. Specific examples of the component (a4) include diaminocyclohexane, diaminodicyclohexylmethane, dimethyl-diaminodicyclohexylmethane, and tetramethyl-diaminodicyclo. Hexylmethane, diaminodicyclohexylpropane, diaminobicyclo[2.2.1]heptane, bis(aminomethyl)-bicyclo[2.2.1]heptane, 3(4), 8(9)- Alicyclic diamines such as bis(aminomethyl)tricyclo[5.2.1.02,6]decane, 1,3-bis(aminomethyl)cyclohexane, isophorone diamine; 2,2- Bis[4-(3-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane and other bis(aminophenoxyphenyl) Propanes; 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether and other diaminodiphenyl ethers ; P-phenylenediamine, m-phenylenediamine and other phenylenediamines; 3,3'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4'-di Diamino diphenyl sulfides such as amino diphenyl sulfide; 3,3'-diamino diphenyl sulfone, 3,4'-diamino diphenyl sulfide, 4,4'-di Diamino diphenyl ketones such as amino diphenyl sulfone; 3,3'-diamino diphenyl ketone, 4,4'-diamino diphenyl ketone, 3,4'-diamino Diaminodiphenyl ketones such as diphenyl ketone; 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenyl Methane and other two Aminodiphenylmethanes; 2,2-bis(3-aminophenyl)propane, 2,2-bis(4-aminophenyl)propane, 2-(3-aminophenyl)-2 -Bis(aminophenyl)propanes such as (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-aminophenyl)-2-(4-aminobenzene Yl)-1,1,1,3,3,3-hexafluoropropane and other bis(aminophenyl)hexafluoropropanes; 1,1-bis(3-aminophenyl)-1-phenylethane Alkanes, 1,1-bis(4-aminophenyl)-1-phenylethane, 1-(3-aminophenyl)-1-(4-aminophenyl)-1-phenylethane Bis(aminophenyl)phenylethanes such as alkanes; 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4 -Bis(aminophenoxy)benzenes such as bis(3-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene; 1,3-bis(3-amino group) Benzoyl)benzene, 1,3-bis(4-aminobenzyl)benzene, 1,4-bis(3-aminobenzyl)benzene, 1,4-bis(4-amine Bis(aminobenzyl) benzene and other 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-dimethylbenzyl)benzene and other bis(aminodimethyl)benzenes; 1,3-bis(3-amino-α,α-bis(trifluoromethyl)benzene Methyl)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; 2,6-bis(3-aminophenoxy)benzonitrile, 2,6-bis(3-aminophenoxy)pyridine, 4,4'-bis(3- Aminophenoxy) biphenyl, 4,4'-bis (4-aminophenoxy) biphenyl and other amine groups Phenoxybiphenyls; Aminophenoxyphenyl such as bis[4-(3-aminophenoxy)phenyl] ketone, bis[4-(4-aminophenoxy)phenyl] ketone Ketones; Aminophenoxyphenyl sulfide such as bis[4-(3-aminophenoxy)phenyl] sulfide, bis[4-(4-aminophenoxy)phenyl] sulfide Class; Bis[4-(3-aminophenoxy)phenyl] phenanthrene, bis[4-(4-aminophenoxy)phenyl] phenanthrene and other aminophenoxyphenyl phenanthrenes; bis[ 4-(3-aminophenoxy)phenyl] ether, bis[4-(4-aminophenoxy)phenyl] ether and other aminophenoxyphenyl ethers; 2,2-bis[ 4-(3-aminophenoxy)phenyl]propane, 2,2-bis[3-(3-aminophenoxy)phenyl]-1,1,1,3,3,3-hexa Aminophenoxyphenylpropanes such as fluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane; Others, 1,3-bis[4-(3-aminophenoxy)benzyl]benzene, 1,3-bis[4-(4-aminophenoxy)benzyl]benzene, 1,4-bis[4-(3-aminophenoxy)benzyl]benzene, 1,4-bis[4-(4-aminophenoxy)benzyl]benzene, 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)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]diphenylbenzene, 4,4'-bis[4-(4-aminophenoxy)phenoxy]diphenylbenzene, 3,3 '-Diamino-4,4'-diphenoxydiphenyl ketone, 3,3'-diamino-4,4'-biphenyloxydiphenyl ketone, 3,3'-di Amino-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-1,1'-spirobisindan, 1,3-bis(3-aminopropyl)tetramethyldisilicon Oxane, 1,3-bis(4-aminobutyl)tetramethyldisilaxane, bis(aminomethyl)ether, bis(2-aminoethyl)ether, bis(3-amino group Propyl) ether, bis[(2-aminomethoxy)ethyl] ether, bis[2-(2-aminoethoxy)ethyl] ether, bis[2-(3-aminopropoxy) Group) ethyl] ether, 1,2-bis(aminomethoxy)ethane, 1,2-bis(2-aminoethoxy)ethane, 1,2-bis[2-(amino group Methoxy)ethoxy]ethane, 1,2-bis[2-(2-aminoethoxy)ethoxy]ethane, ethylene glycol bis(3-aminopropyl)ether, di Ethylene glycol bis(3-aminopropyl) ether, triethylene glycol bis(3-aminopropyl) ether, ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane Alkanes, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane Alkanes, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, etc.; and two or more kinds can be combined. The amount of the component (a4) used is not particularly limited. When all diamine components are set to 100 mol%, it is generally less than 75 mol%.

The component (A1) can be produced by various well-known methods. For example, generally, at a temperature of about 60 to 120°C (preferably 80 to 100°C), the components (a1) and (a2), and optionally the components (a3) and/or (a4) Polymerization addition reaction is carried out for about 0.1 to 2 hours (preferably 0.1 to 0.5 hours) to obtain polyamidoamine. Then, as long as it is further at a temperature of about 80 to 250°C (preferably 100 to 200°C), the The polyamide can be subjected to an imidate reaction, that is, a dehydration ring-closure reaction for about 0.5 to 50 hours (preferably 1 to 20 hours).

In this polymerization addition reaction and amide imidization reaction, various well-known reaction catalysts, dehydrating agents, and component (3) described later 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, picoline, and isoquinoline, etc. ; And more than two kinds can be combined. Examples of the dehydrating agent include aliphatic acid anhydrides such as acetic anhydride and aromatic acid anhydrides such as benzoic acid anhydride, and two or more types can be combined. As the component (3), aprotic polar solvents are preferred, and cyclohexanone and methylcyclohexane are particularly preferred.

The ring closure rate of the amide imide of the component (A1) is not particularly limited, but it is generally 70% or more, preferably 85 to 100%. "Acetylene imide ring closure rate" means the content of cyclic imide bonds (the same below) and can be determined by various spectroscopic means such as nuclear magnetic resonance (NMR) or infrared (IR) spectroscopic analysis.

The number-average molecular weight of the component (A1) (referred to as a value converted to polystyrene measured by colloidal permeation chromatography. The same applies hereinafter) is not particularly limited, but is generally about 4000 to 19000, preferably 6500 to Around 14000. By making the number average molecular weight greater than 4000, there is a tendency to make the heat-resistant adhesiveness of the adhesive layer good, and, by making the number average molecular weight less than 19000, there is a tendency to make the adhesive layer have a low loss elastic modulus It also makes its low dielectric properties good.

As other physical properties of the component (A1), a softening point can be mentioned. Softening point, using a commercially available measuring device ("ARES-2KSTD-FCO-STD", manufactured by Rheometric Scientific Corporation). Specifically, in the viscoelastic curve of the component (A1), the temperature at which the rigid modulus starts to decrease is regarded as the softening point. The value of the softening point is not particularly limited, but is generally about 20 to 200°C, preferably about 50 to 120°C. If the softening point is greater than 20°C, there will be a tendency to make the heat-resistant adhesiveness of the adhesive layer good, and if the softening point is less than 200°C, there will be a tendency that the adhesive layer can be reduced in elastic modulus , And also make its low dielectric properties good.

The concentration of the terminal acid anhydride group of the component (A1) is not particularly limited, but it is generally about 2,500 to 20,000 eq/g, preferably about 3,000 to 10,000 eq/g.

The component (A2) is a primary monoamine represented by the general formula X ¹ -NH ₂ (where X ¹ represents a hydrocarbon group having 1 to 22 carbon atoms), and by using this component (A2), the adhesive layer can be maintained Heat resistance and low dielectric properties, and can improve its fluidity.

Examples of the hydrocarbon group having 1 to 22 carbon atoms include an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 1 to 22 carbon atoms, and an aromatic group. The aromatic group may be an aromatic group having the alkyl group and/or the alkenyl group as a substituent.

The terminal structure of the component (1) is formed by reacting the component (A2) with the terminal acid anhydride group of the component (A1).

(上述式中，X¹表示碳數1~22的烴基。)

(In the above formula, X ¹ represents a hydrocarbon group having 1 to 22 carbon atoms.)

The component (A2) is preferably derived from the general formula X ² -NH ₂ (where X ² represents a linear, branched or cyclic alkyl group or aromatic group having 1 to 22 carbon atoms) Represents a first-level monoamine. The terminal structure of the component (1) is formed by reacting the amine with the terminal acid anhydride group of the component (A1).

(上述式中，X²表示碳數1~22的直鏈狀、分枝狀或環狀的烷基、或芳香族基。)

(In the above formula, X ² represents a linear, branched or cyclic alkyl group having 1 to 22 carbon atoms, or an aromatic group.)

As the aforementioned primary monoamine, specifically, examples include ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, secondary butylamine, tertiary butylamine, Amylamine, isoamylamine, tertiary amylamine, n-octylamine, n-decylamine, isodecylamine, n-tridecylamine, n-dodecylamine, n-hexadecylamine , And primary alkyl monomers such as n-octadecylamine Amines; and, primary aryl monoamines such as aniline, phenoxyaniline, and methylaniline; these primary monoamines may also be composed of two or more types. For example, when the primary alkyl monoamine is derived from animals or plants, it may be a mixture of plural primary alkyl monoamines with different carbon numbers. Also, as such a mixture, a mixture of a primary monoamine and a primary arylamine can be used. In this primary amine, from the viewpoint of being able to maintain the heat-resistant adhesiveness and low dielectric properties of the adhesive layer and reduce its loss elastic modulus, it is preferably at least one selected from the group consisting of : Primary alkyl monoamine and primary aryl monoamine with an alkyl group having a carbon number of about 4 to 22 (preferably about 10 to 20). In particular, the primary aryl monoamine has the following tendency: it also contributes to the compatibility (transparency) of the adhesive layer of the present invention.

Examples of commercially available products of this primary alkyl monoamine include: LIPOMIN CD (coconut alkyl amine), LIPOMIN OD (oleyl amine), LIPOMIN TD (tallow alkyl amine), LIPOMIN 8D (octyl amine), LIPOMIN 12D (dodecylamine), LIPOMIN 18D (octadecylamine), FARMIN CS (coconut amine), FARMIN 08D (octylamine), FARMIN 20D (dodecylamine), FARMIN 80 (stearin) Amine), FARMIN 86T (stearylamine), FARMIN T (tallowamine), etc.

The amount of component (A2) used is not particularly limited. From the viewpoint of the balance of low-loss elastic modulus of the adhesive layer, heat-resistant adhesiveness, and low dielectric properties, it is 1 mole relative to component (A1). The terminal acid anhydride group, the general component (A2) is in the range of about 0.8 to 1.2 moles, preferably in the range of about 0.9 to 1.1 moles.

The method of blocking the terminal acid anhydride group of the component (A1) by the component (A2) is not particularly limited, and various well-known means can be adopted. Specifically, for example, as long as the component (A2) obtained by the above-mentioned production method is added to the component (A2) in the aforementioned amount, generally, it is performed at about 80 to 250°C (preferably 100 to 200°C). The imidization reaction may be 0.5 to 50 hours (preferably 1 to 20 hours). In addition, in the amide imidization reaction, the aforementioned reaction catalyst, the aforementioned dehydrating agent, and the component (3) described later may be used as necessary.

The ring closure rate of the amide imide of the component (1) is not particularly limited, but it is generally 70% or more, preferably 85 to 100%.

The number average molecular weight of the component (1) is not particularly limited, but it is generally about 5,000 to 20,000, preferably about 7,500 to 15,000. By making the number average molecular weight greater than 5000, there is a tendency to make the heat-resistant adhesiveness of the adhesive layer good, and, by making the number average molecular weight less than 20,000, there is a tendency that the adhesive layer can be elasticized with low loss , And also make its low dielectric properties good.

The value of the softening point of the component (1) is not particularly limited, but it is generally about 20 to 200°C, preferably about 50°C to 120°C. If the softening point is greater than 20°C, there will be a tendency to make the heat-resistant adhesiveness of the adhesive layer good, and if the softening point is less than 200°C, there will be a tendency that the adhesive layer can be reduced in elastic modulus , And also make its low dielectric properties good.

The component (1) is preferably used as a solution, and the concentration of non-volatile components is generally about 10 to 60% by weight.

化合物、雙馬來醯胺化合物及氰酸酯化合物。 As the component (2), as long as it can exhibit performance as a crosslinking agent of polyimide, various known components can be used without particular limitation. Specifically, for example, it is preferably at least one selected from the group consisting of epoxy compounds, benzo

Compounds, bismaleamide compounds and cyanate compounds.

骨架之環氧化合物、含茀骨架之環氧化合物、線狀脂肪族環氧化合物、脂環式環氧化合物、環氧丙基胺型環氧化合物、三苯酚苯酚甲烷型環氧化合物、烷基改質三苯酚甲烷型環氧化合物、聯苯型環氧化合物、含雙環戊二烯骨架之環氧化合物、含萘骨架之環氧化合物、芳基伸烷型環氧化合物、四環氧丙基二甲苯二胺、以二聚物酸將這些環氧化合物改質而成的改質環氧化合物、二聚物酸二環氧丙酯等；且可將2種以上組合。又，作為市售品，可列舉例如：三菱化學股份有限公司製造的「jER828」或「jER834」、「jER807」；新日鐵化學股份有限公司製造的「ST-3000」；大賽璐化學工業股份有限公司製造的「CELLOXIDE 2021P」；新日鐵化學股份有限公司製造的「YD-172-X75」；三菱氣體化學股份有限公司製造的「TETRAD-X」等。其中，從耐熱黏著性、吸濕焊料耐 熱性及低介電特性的平衡的觀點而言，較佳是選自由下述所組成之群組中的至少一種：雙酚A型環氧化合物、雙酚F型環氧化合物、氫化雙酚A型環氧化合物、及脂環式環氧化合物。 Examples of the epoxy compound include phenol novolac epoxy compounds, cresol novolac epoxy compounds, bisphenol A epoxy compounds, bisphenol F epoxy compounds, and bisphenol S epoxy compounds. , Hydrogenated bisphenol A epoxy compound, hydrogenated bisphenol F epoxy compound, diphenylethylene epoxy compound, containing three

Epoxy compound of skeleton, epoxy compound containing stilbene skeleton, linear aliphatic epoxy compound, alicyclic epoxy compound, epoxypropylamine epoxy compound, triphenolphenol methane epoxy compound, alkyl group Modified triphenol methane type epoxy compound, biphenyl type epoxy compound, epoxy compound containing dicyclopentadiene skeleton, epoxy compound containing naphthalene skeleton, aryl alkylene type epoxy compound, tetra epoxypropyl di Toluene diamine, modified epoxy compound obtained by modifying these epoxy compounds with a dimer acid, diglycidyl 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.; 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, from the viewpoint of the balance of heat-resistant adhesiveness, moisture-absorbing solder heat resistance, and low dielectric properties, at least one selected from the group consisting of bisphenol A-type epoxy compounds, bis Phenol F-type epoxy compound, hydrogenated bisphenol A-type epoxy compound, and alicyclic epoxy compound.

In particular, the tetraglycidoxyxylenediamine having the following structure has good compatibility with the component (1). In addition, if the tetraglycidoxypropyl xylenediamine is used, it is easy to make the adhesive layer have a low-loss elastic modulus, and it also has good heat-resistant adhesive properties and low dielectric properties.

(式中，Z表示伸苯基或環己烯基)

(In the formula, Z represents phenylene or cyclohexenyl)

改質苯酚酚醛清漆樹脂、含酚性羥基之膦氮烯(大塚化學股份有限公司製造的商品名「SPH-100」等)等酚系硬化劑、環狀膦氮烯系化合物；馬來酸改質松香或其氫化物等松香系交聯劑等；且可將2種以上組合。其中，較佳是酚系硬化劑，特佳是含酚性羥基之膦氮烯系硬化劑。這些硬化劑的使用量，並無特別限制，一般而言，當將本發明的黏著劑的固體成分設為100重量%時，是0.1~120重量%左右，較佳是10~40重量%左右。 When an epoxy compound is used as the component (2), various well-known hardeners 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 alcohol Anhydride-based hardeners such as dicyclohexene dicarboxylic anhydride, 3-dodecenyl succinic anhydride, octenyl succinic anhydride; dicyandiamine (DICY), aromatic diamine (trade name "LonzacureM-DEA", "LonzacureM-DETDA" etc. are all manufactured by Lonza Japan Ltd.), aliphatic amines and other amine hardeners; phenol novolak resin, cresol novolak resin, bisphenol A type novolak resin, three

Modified phenol novolak resin, phenolic hydroxyl group-containing phosphazene (trade name "SPH-100" manufactured by Otsuka Chemical Co., Ltd.) and other phenolic hardeners, cyclic phosphazene compounds; maleic acid modification Rosin-based cross-linking agent such as high-quality rosin or its hydride; and more than two types can be combined. Among them, a phenolic hardener is preferred, and a phosphazene-based hardener containing a phenolic hydroxyl group is particularly preferred. The use amount of these hardeners is not particularly limited. Generally speaking, when the solid content of the adhesive of the present invention is 100% by weight, it is about 0.1 to 120% by weight, preferably about 10 to 40% by weight. .

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, ginseng (dimethylaminomethyl)phenol; 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole Imidazoles; organic phosphines such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, and phenylphosphine; tetraphenylphosphnium tetraphenylphosphonate (tetraphenylphosphnium tetraphenylborate), tetrabenzene Boronic acid 2- Tetraphenylborate, such as ethyl-4-methylimidazole, tetraphenylboronic acid N-methylmorpholine, etc.; and two or more types can be combined. In addition, the amount of the reaction catalyst used is not particularly limited. Generally speaking, when the solid content of the adhesive of the present invention is 100% by weight, it is about 0.01 to 5% by weight.

化合物，可列舉例如：6,6-(1-甲基亞乙基)雙(3,4-二氫-3-苯基-2H-1,3-苯并

)、6,6-(1-甲基亞乙基)雙(3,4-二氫-3-甲基-2H-1,3-苯并

)等；且可將2種以上組合。再者，在環的氮上可鍵結有苯基、甲基、環己基等。又，作為市售品，可列舉例如四國化成工業股份有限公司製造的「Benzoxazine F-a型」或「Benzoxazine P-d型」、AIR WATER INC.製造的「RLV-100」等。 As the aforementioned benzo

Compounds include, for example: 6,6-(1-methylethylene)bis(3,4-dihydro-3-phenyl-2H-1,3-benzo

), 6,6-(1-methylethylene)bis(3,4-dihydro-3-methyl-2H-1,3-benzo

) Etc.; and more than two types can be combined. Furthermore, a phenyl group, a methyl group, a cyclohexyl group, etc. may be bonded to the nitrogen of the ring. In addition, examples of commercially available products include "Benzoxazine Fa type" or "Benzoxazine Pd type" manufactured by Shikoku Chemical Industry Co., Ltd., and "RLV-100" manufactured by AIR WATER INC., and the like.

Examples of the bismaleimide compound include 4,4′-diphenylmethane bismaleimide, m-phenylene bismaleimide, and bisphenol A diphenyl ether bismaleimide. Laimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-benzidine Bis-maleimide, 1,6'-bismaleimide-(2,2,4-trimethyl)hexane, 4,4'-diphenyl ether bismaleimide, 4,4'-Diphenyl bismaleimide, etc.; more than two types can be combined. In addition, examples of commercially available products include "BAF-BMI" manufactured by JFE Chemical Corporation.

Examples of the cyanate compound include 2-allylphenol cyanate, 4-methoxyphenol cyanate, 2,2-bis(4-cyanophenol)-1,1,1 ,3,3,3-hexafluoropropane, bisphenol A cyanate, diene Propyl bisphenol A cyanate, 4-phenylphenol cyanate, 1,1,1-ginseng (4-cyanophenyl)ethane, 4-cumyl phenol cyanate, 1, 1-bis(4-cyanophenyl)ethane, 4,4'-bisphenol cyanate, and 2,2-bis(4-cyanophenyl)propane, etc.; and more than two types can be used combination. In addition, examples of commercially available products include "PRIMASET BTP-6020S (manufactured by Lonza Japan Ltd.)" and the like.

As the component (3), various known solvents can be used without limitation. Specific examples include N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, dimethylsulfoxide, N-methylcaprolactam, methyl Aprotic polar solutions such as triethylene glycol dimethyl ether and methyl diglyme; or, alicyclic solvents such as cyclohexanone and methylcyclohexane; methanol, ethanol, propanol, benzyl alcohol, methyl alcohol Alcohol solvents such as phenol; aromatic solvents such as toluene; etc.; and two or more kinds can be combined.

The adhesive of the present invention may be blended with the aforementioned ring-opening esterification reaction catalyst or dehydrating agent, plasticizer, weathering agent, antioxidant, heat stabilizer, lubricant, antistatic agent, whitening agent, coloring as needed Additives, conductive agents, release agents, surface treatment agents, viscosity modifiers, phosphorus flame retardants, flame retardant fillers, silica fillers, fluorine fillers and other additives.

The amount of component (1), component (2), and component (3) used is not particularly limited. From the viewpoint of the balance of low-loss elastic modulus of the adhesive layer, heat-resistant adhesiveness, and low dielectric properties, relative With respect to 100 parts by weight of component (1), preferably, component (2) is 11 to 900 parts by weight, and component (3) is 150 to 900 parts by weight.

The film-shaped adhesive material of the present invention is an article composed of the polyimide-based adhesive of the present invention. Specifically, it is, for example, an article in which the adhesive is applied to an appropriate support and heated to evaporate the component (3), thereby hardening it, and then peeled off from the support. The thickness of the adhesive material is not particularly limited, but is generally about 3 to 40 μm. As the support, the following support may be mentioned.

The adhesive sheet of the present invention is an article, and its constituent elements include an adhesive layer composed of the polyimide-based adhesive of the present invention or the film-shaped adhesive material of the present invention; and, a supporting film. Examples of the support include the following plastic films: polyester, polyimide, polyimide-silica mixture, polyethylene, polypropylene, polyethylene terephthalate, and polynaphthalene 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.) etc. In addition, when the polyimide-based adhesive of the present invention is coated on the support, the aforementioned coating means can be used. The thickness of the coating layer is also not particularly limited. Generally speaking, the thickness after drying should be in the range of about 1 to 100 μm, preferably in the 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-coated copper foil of the present invention is an article, and its constituent elements include the adhesive layer of the present invention and a copper foil. in particular, It is the following article: it is obtained by coating or sticking the polyimide-based adhesive or the film-like adhesive material on a copper foil. Examples of the copper foil include rolled copper foil and electrolytic copper foil. The thickness is not particularly limited, but is generally about 1 to 100 μm, preferably about 2 to 38 μm. In addition, the copper foil may be a copper foil subjected to various surface treatments (roughening, rust prevention, etc.). Examples of the anti-rust treatment include so-called mirror treatment such as plating treatment using a plating solution containing nickel, zinc, tin, and the like, or chromate treatment. In addition, as the coating means, the aforementioned method may be mentioned. In addition, the adhesive layer of the copper foil with resin may not be hardened, and may be partially or completely cured under heating. The partially hardened adhesive layer is in a state 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 with resin on both sides may be prepared by further bonding copper foil on the adhesive surface of the copper foil with resin.

The copper-clad laminate of the present invention is an article which is formed by laminating a copper foil with resin of the present invention and a copper foil or an insulating sheet, and is also called a copper foil substrate (CCL, copper clad laminate) . Specifically, it is an article obtained by pressing the copper foil with resin of the present invention on at least one side or both sides of various well-known copper foils or insulating sheets under heating. When pasting on one side, a different one from the resin-coated copper foil of the present invention may be pressed on the other side. In addition, the number of resin-coated copper foils and insulating sheets in the copper-clad laminate is not particularly limited. In addition, the insulating sheet is preferably a prepreg. Prepreg refers to a sheet-like material, which is a reinforcing material that impregnates resin with glass cloth Material and harden it up to the B stage (Japanese Industrial Standard (JIS) C 5603). As the resin, insulating resins such as polyimide resin, phenol resin, epoxy resin, polyester resin, liquid crystal polymer, and polyaramide resin 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, and are generally about 150 to 280°C (preferably about 170°C 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 formed by forming a circuit pattern on the copper foil surface of the copper-clad laminate of the present invention. As means for patterning, for example, a subtractive method or a semi-additive method may be mentioned. Examples of the semi-additive method include the following method: patterning 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 using an alkaline solution Perform etching. In addition, 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 substrate and stacking the same printed wiring board or other known printed wiring boards or printed circuit boards thereon. At the time of lamination, in addition to the polyimide-based adhesive of the present invention, other well-known polyimide-based adhesives can also be used. In addition, the number of build-up layers in the multilayer substrate is not particularly limited. In addition, each layer can be inserted with a through hole, and the inside is plated. The line width/pitch ratio of the aforementioned 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 aforementioned 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: the core substrate is a printed circuit board or a printed circuit board, the adhesive layer of the present invention, and other substrates are also a printed circuit board or a 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 the manufacturing method including the following steps 1 and 2.

Step 1: By contacting the polyimide-based adhesive or film-like adhesive material of the present invention with at least one side of the core substrate, that is, a printed wiring board or a printed circuit board, an adhesive layer-attached layer is manufactured Substrate steps.

Step 2: On the substrate with the adhesive layer, a printed circuit board or a printed circuit board is laminated, and the step of pressing under heating and pressure is performed.

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 polyimide-based adhesive or film-like adhesive material of the present invention into contact with the adherend is not particularly limited, and various well-known coating methods can be used, such as curtain coaters, Roll coater, laminator, laminator, etc.

The heating temperature and the pressing time in step 2 are not particularly limited, and in general, it is preferable to: (a) at least the polyimide-based adhesive or film-like adhesive material of the present invention and the core substrate are at least After one of the surfaces is contacted, it is generally heated to about 70 to 200°C, and it takes about 1 to 10 minutes to perform the hardening reaction. (b) Then it is further subjected to heat treatment to allow the hardening reaction of the component (2) to proceed. The treatment is generally about 150℃~250℃, about 10 minutes~3 hours. In addition, the pressure is not particularly limited. For 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, comparative examples, and reference examples, but the scope of the present invention is not limited to these examples and comparative examples. In addition, in each case, unless otherwise noted, parts and% are based on weight. In addition, the number average molecular weight is a value obtained using a commercially available measuring machine ("HLC-8220GPC", manufactured by Tosoh Corporation), and the softening point is using a commercially available measuring machine ("ARES-2KSTD-FCO-STD ", obtained by Rheometric Scientfic).

<Synthetic acid anhydride terminal polyimide> (Production Example 1)

225.00g of 3,3',4,4'-diphenyl ketonetetracarboxylic dianhydride (trade name "BTDA-PF", Evonik) was put in a reaction vessel equipped with a stirrer, water trap, thermometer and nitrogen introduction tube Japan Co., Ltd.), 1046.25 g of cyclohexanone, and 209.25 g of methylcyclohexane, and heated up to 60°C. Then, 345.93 g of dimer diamine (trade name "PRIAMINE 1075", manufactured by Croda Japan KK) was added, and the amide imidation reaction was carried out at 130°C for 12 hours, thereby obtaining an acid anhydride group-terminated polyimide ( A1-1) (hereinafter also referred to as ingredients (A1-1)) solution (non-volatile content 31.0%). The molar ratio of the acid component/amine component of this component (A1-1) was 1.08, the number average molecular weight was 8,500, and the softening point was 70°C.

(Production Example 2)

In the same reaction vessel as in Production Example 1, 755.63 g of the solution of the aforementioned component (A1-1) was added, and the solvent was distilled off under reduced pressure until the non-volatile component became 34.4%. Then, 2.76 g of octylamine (trade name "LIPOMIN 8D", manufactured by Lion Specialty Chemicals Co., Ltd.) as a component (A2) was further added, and the reaction was carried out at 140°C for 16 hours, thereby obtaining a terminal-blocked polymer A solution (35.9% of non-volatile content) of acetylenimine (1-1) (hereinafter also referred to as component (1-1)). The molar ratio of the terminal anhydride group/octylamine of this component (1-1) is 1.0, the number average molecular weight is 10,000, and the softening point is 70°C.

(Production Example 3)

In the same reaction vessel as in Production Example 1, 755.63 g of the solution of the aforementioned component (A1-1) was added, and the solvent was distilled off under reduced pressure until the nonvolatile component became 34.0%. Then, 4.69g of coconut oil amine (trade name "FARMIN CS", manufactured by Kao Co., Ltd.) was further added as the component (A2), and the main alkyl composition was C12: 51%, C14: 19%, C16: 8%, C18: 6%), and the reaction was carried out at 140°C for 16 hours, thereby obtaining a solution (non-volatile component 35.2%) of terminal-blocked polyimide (1-2) (hereinafter also referred to as component (1-2)) . The molar ratio of the anhydride end group/octylamine of this component (1-2) is 1.0, the number average molecular weight is 10500, and the softening point is 70°C.

(Production Example 4)

In the same reaction vessel as in Production Example 1, 755.63 g of the solution of the aforementioned component (A1-1) was added, and the solvent was distilled off under reduced pressure until the non-volatile component became 34.2%. Then, 1.99 g of aniline (manufactured by Tokyo Chemical Industry Co., Ltd.) as a component (A2) was further added, and the reaction was carried out at 140° C. for 16 hours, thereby obtaining terminal-blocked polyimide (1-3) (hereinafter also A solution called non-volatile component (35.4%) called component (1-3). The molar ratio of the anhydride end group/aniline of this component (1-3) is 1.0, the number average molecular weight is 10,000, and the softening point is 70°C.

(Production Example 5)

In the same reaction vessel as in Production Example 1, 490.00 g of BTDA-PF, 2597.00 g of cyclohexanone, and 519.40 g of methylcyclohexane were charged and heated to 60°C. Then, 489.68g of PRIAMINE 1075 and 429.69g of α,ω-bis(3-aminopropyl) polydimethylsiloxane (trade name "KF-8010", manufactured by Shin-Etsu Chemical Industry Co., Ltd.) were added, and It took 12 hours at 130°C to carry out the amide imidization reaction, thereby obtaining a solution (30.1% of non-volatile ingredients) of an acid anhydride group-terminated polyimide (A1-2) (hereinafter also referred to as ingredient (A1-2)) . The molar ratio of the acid component/amine component of this component (A1-2) is 1.09, the number average molecular weight is 9,500, and the softening point is 30°C.

(Production Example 6)

In the same reaction vessel as in Production Example 1, 1400.00 g of a solution of the component (A1-2) was added, and the solvent was distilled off under reduced pressure until the nonvolatile content became 34.1%. Then, further input 3.81g LIPOMIN 8D, and reacted at 140°C for 12 hours, after which 346.55 g of cyclohexanone was added, thereby obtaining a solution of terminal-blocked polyimide (1-4) (hereinafter also referred to as component (1-4)) ( Non-volatile content 35.0%). The molar ratio of the anhydride end group/amine component of this component (1-4) is 1.0, the number average molecular weight is 11,800, and the softening point is 30°C.

(Production Example 7)

In the same reaction vessel as in Production Example 1, 310.00 g of 4,4'-[propan-2,2-diylbis(1,4-phenyleneoxy)]bis(phthalic anhydride) (Trade name "BisDA1000", manufactured by Evonik Japan Co., Ltd.), 992.00 g of cyclohexanone, and 124.00 g of methylcyclohexane, and heated up to 60°C. Then, 306.59 g of PRIAMINE 1075 was added, and it took 15 hours at 130° C. to carry out the amide imidization reaction, thereby obtaining an acid anhydride group-terminal polyimide (A1-3) (hereinafter also referred to as component (A1-3)) Solution (35.7% of non-volatile components). The molar ratio of the acid component/amine component of this component (A1-3) was 1.05, the number average molecular weight was 15,000, and the softening point was 80°C.

(Production Example 8)

In the same reaction vessel as in Production Example 1, a solution of 1453.17 g of the component (A1-3) was added, and the solvent was distilled off under reduced pressure until the nonvolatile content became 36.6%. Subsequently, 3.08 g of LIPOMIN 8D was further added, and the reaction was carried out at 130° C. for 13 hours, thereby obtaining a solution (non-volatile) of the terminal-blocked polyimide (1-5) (hereinafter also referred to as component (1-5)). Composition 38.7%). The acid anhydride terminal group/amine composition of this component (1-5) The molar ratio is 1.0, the number average molecular weight is 16000, and the softening point is 80°C.

(Production Example 9)

In the same reaction vessel as in Production Example 1, 1650.00 g of 4,4'-[propan-2,2-diylbis(1,4-phenyleneoxy)]bis(phthalic anhydride) (Trade name "BisDA1000", manufactured by SABIC JAPAN LLC), 4292.22 g of cyclohexanone, and heated to 60°C. Then, 1068.95 g of PRIAMINE 1075, 1289.47 g of 1,2-dimethoxyethane, and 716.37 g of methylcyclohexane were added, and the amide imidation reaction was carried out at 130° C. for 15 hours, thereby obtaining an acid anhydride A solution (32.0% of non-volatile component) of a polyimide (A1-4) (hereinafter also referred to as component (A1-4)) at the base end. The molar ratio of the acid component/amine component of this component (A1-4) is 1.09, the number average molecular weight is 16000, and the softening point is 100°C.

(Production Example 10)

In the same reaction vessel as in Production Example 1, a solution of 6506.92 g of the component (A1-4) was added, and the solvent was distilled off under reduced pressure until the nonvolatile content became 34.6%. Then, 27.25 g of LIPOMIN 8D was further added, and the reaction was carried out at 130° C. for 14 hours, thereby obtaining a solution (non-volatile) of the terminal-blocked polyimide (1-6) (hereinafter also referred to as component (1-6)). Ingredients 35.7%). The molar ratio of the anhydride end group/amine component of this component (1-6) is 1.0, the number average molecular weight is 16,500, and the softening point is 100°C.

<Mixed Polyimide Adhesive> (Example 1)

A solution of 100.00 g of component (1-1) and 8.98 g of N,N,N',N'-tetraglycidoxypropylxylenediamine (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name "TETRAD-X" ", epoxy equivalent of 95g/eq) and 20.00g of toluene, and uniformly stirred, thereby obtaining a 34.8% non-volatile adhesive.

(Example 2)

A solution of 100.00 g of the component (1-2), 8.80 g of TETRAD-X and 20.00 g of toluene were mixed and stirred uniformly, thereby obtaining a 34.2% non-volatile adhesive.

(Reference example 1)

A solution of 100.00 g of the component (1-3), 8.85 g of TETRAD-X and 20.00 g of toluene were mixed and stirred uniformly, thereby obtaining a 34.3% non-volatile adhesive.

(Example 3)

A solution of 100.00 g of the component (1-4), 8.75 g of TETRAD-X and 20.00 g of toluene were mixed and stirred uniformly, thereby obtaining a 34.0% non-volatile adhesive.

(Example 4)

A solution of 100.00 g of the component (1-5), 9.68 g of TETRAD-X, and 30.00 g of toluene were mixed and stirred uniformly, thereby obtaining a 34.6% non-volatile adhesive.

(Example 5)

A solution of 100.00 g of the component (1-6), 8.93 g of TETRAD-X and 20.00 g of toluene were mixed and stirred uniformly, thereby obtaining a 34.6% non-volatile adhesive.

(Comparative example 1)

A solution of 100.00 g of the component (A1-1), 7.75 g of TETRAD-X and 10.00 g of toluene were mixed and stirred uniformly, thereby obtaining a 32.9% nonvolatile component adhesive.

(Comparative example 2)

A solution of 100.00 g of the component (A1-2), 7.53 g of TETRAD-X and 10.00 g of toluene were mixed and stirred uniformly, thereby obtaining a 32.0% non-volatile adhesive.

(Comparative example 3)

A solution of 100.00 g of the component (A1-3), 8.93 g of TETRAD-X and 20.00 g of toluene were mixed and stirred uniformly, thereby obtaining a 34.6% non-volatile adhesive.

(Comparative example 4)

A solution of 100.00 g of the component (A1-4), 8.00 g of TETRAD-X, and 10.00 g of toluene were mixed and stirred uniformly, thereby obtaining a 33.9% non-volatile adhesive.

<Measurement of loss elastic modulus of adhesive layer>

The adhesive of Example 1 was coated on NAFLON PTFE tape No. 9001 (manufactured by NICHIAS Corporation), dried at room temperature for 12 hours, and then dried at 150° C.×5 minutes to prepare an adhesive sheet of about 20 μm .

Then, the adhesive sheet was folded to prepare 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 loss elastic modulus. Sex. Furthermore, the temperature increase rate is 10°C/min. The results are shown in Table 1 and Figure 1. In addition, this measurement was also performed on the adhesives of other examples, comparative examples and reference examples. The results are shown in Table 1.

<Measurement of dielectric constant and dielectric loss tangent of the adhesive layer>

The adhesive of Example 1 was coated on NAFLON PTFE tape No. 9001 (manufactured by NICHIAS Corporation), dried at room temperature for 12 hours, and then cured at 200°C for 1 hour, thereby obtaining an adhesive with a film thickness of 50 μm Flakes.

Then, the dielectric constant and dielectric loss tangent at 10 GHz were measured for this adhesive sheet in accordance with JIS C2565 using a commercially available dielectric constant measuring device (cavity resonator type, manufactured by AET INC.). In addition, the adhesives of other examples, comparative examples and reference examples were also measured in the same manner. The results are shown in Table 1.

<Measure the heat-resistant adhesion of the adhesive layer>

Using a gap coater, the adhesive of Example 1 was applied to an electrolytic copper foil of 18 μm thickness (trade name “F2-WS”, Furukawa Electric) so that the film thickness after drying became 15 μm. Manufactured by Industrial Co., Ltd. 25.4 cm in width on a mirror surface, and then dried at 150° C. for 5 minutes, thereby obtaining a copper foil with resin.

Then, F2-WS was laminated on the adhesive surface of the resin-coated copper foil from the mirror side, and heated and pressed under the conditions of pressure 4.5 MPa, 160° C., and 1 hour, thereby preparing a bonded sample . Then, the sample was subjected to a heat treatment at 200° C.×60 hours in the atmosphere, and then the peel strength (N/cm) was measured in accordance with JIS C 6481 (Test method for copper-clad laminate for flexible printed wiring boards). In addition, the adhesives of other examples, comparative examples and reference examples were also measured in the same manner. The results are shown in Table 1.

Claims (19)

A polyimide-based adhesive, comprising: terminal modified polyimide (1), which is a reactant of an acid anhydride group terminal polyimide (A1) and a primary monoamine (A2), the acid anhydride group terminal Polyimide (A1) is a reactant of aromatic tetracarboxylic anhydride (a1) and monomer group (α) containing dimer diamine (a2), and the primary monoamine (A2) is of the general formula X ¹ -NH ₂ represents, in this general formula, X ¹ represents a linear, branched or cyclic alkyl group having 1 to 22 carbon atoms; a cross-linking agent (2); and, an organic solvent (3) . The polyimide-based adhesive according to claim 1, wherein the component (a1) is represented by the following general formula,

In the above formula, Y represents a single bond, -SO ₂ -, -CO-, -O-, -OC ₆ H ₄ -C(CH ₃ ) ₂ -C ₆ H ₄ -O- or -COO-Y ¹ -OCO -, and Y ¹ represents -(CH ₂ ) _l -(l=1~20) or -H ₂ C-HC(-OC(=O)-CH ₃ )-CH ₂ -. The polyimide-based adhesive according to claim 1 or 2, The molar ratio of the component (a1) to the component (a2) is 1<[(a1)/(a2)]<1.2. The polyimide-based adhesive according to claim 1, wherein the monomer group (α) further includes a diamine polysiloxane (a3). The polyimide-based adhesive according to claim 4, wherein the ratio of moles of the component (a1) to the total moles of the component (a2) and the component (a3) is 1<[(a1) /[(A2)+(a3)]]<1.2. The polyimide-based adhesive according to claim 4 or 5, wherein the ratio of the mole of the component (a2) to the total mole of the component (a2) and the component (a3) is 0.3<[( a2)/[(a2)+(a3)]]<1. The polyimide-based adhesive according to claim 1, wherein the amount of the component (A2) used is 0.8 to 1.2 mol per 1 mol of the terminal anhydride group of the component (A1). The polyimide-based adhesive according to claim 1, wherein the component (2) contains at least one selected from the group consisting of: epoxy compound, benzo

Compounds, bismaleamide compounds and cyanate compounds. The polyimide-based adhesive according to claim 8, wherein the epoxy compound contains tetraglycidoxyxylenediamine having the following structure,

In the above formula, Z represents phenylene or cyclohexenyl. The polyimide-based adhesive according to claim 1, wherein the component (1) is 100 parts by weight in terms of solid content, the component (2) is 11 to 900 parts by weight, and the component (3 ) Is 150 to 900 parts by weight. A film-like adhesive material composed of the polyimide-based adhesive according to any one of claims 1 to 10. An adhesive layer composed of the polyimide-based adhesive according to any one of claims 1 to 10 or the film-shaped adhesive material according to claim 11. An adhesive sheet, as its constituent elements, includes: the adhesive layer as described in claim 12 and a supporting film. A copper foil with resin as its constituent elements includes the adhesive layer and the copper foil as described in claim 12. A copper-clad laminate, as its constituent elements, includes the copper foil with resin as described in claim 14 and a copper foil. A copper-clad laminate, as its constituent elements, includes: The copper foil with resin and an insulating sheet as described in claim 14. A printed wiring board formed by forming a circuit pattern on the copper foil surface of the copper-clad laminate according to claim 15 or 16. A multilayer circuit board, as its constituent elements, including: the core substrate is a printed circuit board or a printed circuit board, the adhesive layer as described in claim 12, and the other substrate is a printed circuit board or a printed circuit board Circuit board. A method for manufacturing a multilayer wiring board, comprising the following steps 1 and 2: Step 1 is by using the polyimide-based adhesive as described in any one of claims 1 to 10 or as described in claim 11 The film-shaped adhesive material mentioned above is in contact with the core substrate, that is, at least one side of a printed wiring board or a printed circuit board, to produce a substrate with an adhesive layer; Step 2 is to attach the adhesive layer On the substrate, a printed circuit board or a printed circuit board is laminated, and the pressing step is performed under heating and pressure.

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