JP6686619B2 - Polyimide adhesive, film adhesive, adhesive layer, adhesive sheet, copper clad laminate and printed wiring board, and multilayer wiring board and method for producing the same - Google Patents

Description

  The present invention includes a polyimide adhesive particularly useful in the production of a multilayer wiring board (MLB: Multi-Layer Board) and a film adhesive made of the adhesive, an adhesive layer obtained from the adhesive, and the adhesive layer. The present invention relates to an adhesive sheet, a copper clad laminate, a printed wiring board, a multilayer wiring board, and a method for manufacturing the multilayer wiring board.

  Flexible Printed Wiring Boards (FPWBs), Printed Circuit Boards (PCBs), and multilayer wiring boards using them are mobile communication devices such as mobile phones and smartphones and their base station devices, It is commonly used in products such as network-related electronic devices such as servers and routers, and large computers.

  In recent years, high-frequency electrical signals have been used in these products to transmit and process large amounts of information at high speed. However, high-frequency signals are very easily attenuated, so transmission loss should be minimized in the multilayer wiring board. A device to suppress it is required.

  As means for suppressing the transmission loss in the multilayer wiring board, for example, when laminating a printed wiring board or a printed circuit board, it is of course excellent in heat-resistant adhesiveness, and the dielectric constant and dielectric loss tangent are both small (hereinafter, It is conceivable to use a polyimide-based adhesive having a low dielectric property (for example, see Patent Documents 1 to 3). Further, the polyimide-based adhesive may be used as a film-shaped adhesive.

  On the other hand, as the products have become smaller, thinner and lighter, electronic parts and semiconductor parts have become smaller and smaller, and even in the flexible wiring boards on which they are mounted, higher definition and higher density have been advanced. ing.

  A multilayer wiring board in which such high-definition / high-density boards are laminated and which has high adhesion reliability can be obtained by, for example, the following method. That is, (1) a polyimide-based adhesive or a polyimide-based film adhesive is brought into contact with one surface of a printed wiring board or a printed circuit board, which is an adherend, to produce a substrate with an adhesive layer, and (2) By heating the substrate with an adhesive layer at a temperature of about 100 to 200 ° C., the adhesive layer is brought into a semi-cured state (so-called B stage), and (3) a printed wiring board or a print is further formed on the adhesive layer of the B stage. This is a method in which circuit boards are laminated and pressure-bonded under heating.

  In the step (2), the B-stage adhesive layer is required to have appropriate fluidity. This is because the adhesive layer is spread over the fine irregularities on the surface of the adherend to reduce the gap as much as possible and prevent defective 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 of the B stage can be evaluated by the loss elastic modulus, and the lower the loss elastic modulus, the better. As a means for lowering the loss elastic modulus, for example, a method of lowering the molecular weight of polyimide which is the main component or introducing an ether bond or a branched structure into the molecule can be considered. However, such a polyimide-containing adhesive layer may flow out from the end portion of the multilayer wiring board in the step (3), or may have insufficient heat-resistant adhesiveness and low dielectric properties.

JP, 2009-299040, A JP, 2014-045076, A JP, 2014-086591, A

  The main object of the present invention is to provide a novel polyimide-based adhesive that provides an adhesive layer having a low loss elastic modulus in the B stage and excellent heat resistance and low dielectric properties.

  It is also a main object of the present invention to provide a novel polyimide film adhesive, which has a low loss elastic modulus in the B stage and gives an adhesive layer having good heat resistance and low dielectric properties.

  As a result of diligent studies, the present inventor has found that the above problem can be solved by an adhesive having a terminal-modified polyimide obtained by reacting a primary monoamine with the terminal acid anhydride group of a predetermined acid anhydride-terminated polyimide as a base resin. It was

  That is, the present invention relates to a polyimide-based adhesive, a film-like adhesive, an adhesive layer, an adhesive sheet, a copper-clad laminate and a printed wiring board, a multilayer wiring board and a method for producing the same, which will be described below.

1. An acid anhydride group-terminated polyimide (A1) which is a reaction product of a monomer group (α) containing an aromatic tetracarboxylic acid anhydride (a1) and a dimer diamine (a2), and a general formula: X ¹ —NH ₂ (wherein , X ¹ represents a hydrocarbon group having 1 to 22 carbon atoms), a terminal modified polyimide (1) which is a reaction product of a primary / primary monoamine (A2),
A cross-linking agent (2),
Including an organic solvent (3),
Polyimide adhesive.

（式中、Ｙは単結合、−ＳＯ_２−、−ＣＯ−、−Ｏ−、−Ｏ−Ｃ_６Ｈ_４−Ｃ（ＣＨ_３）_２−Ｃ_６Ｈ_４−Ｏ−又は−ＣＯＯ−Ｙ^１−ＯＣＯ−（Ｙ^１は−（ＣＨ_２）_ｌ−（ｌ＝１〜２０）若しくは−Ｈ_２Ｃ−ＨＣ（−Ｏ−Ｃ（＝Ｏ）−ＣＨ_３）−ＣＨ_２−を示す。）を表す。） 2. The polyimide adhesive according to item 1, wherein the component (a1) is represented by the following general formula.

(Wherein, Y represents a single _{bond, -SO 2 -, - CO -} , - O -, - O-C 6 H 4 -C (CH 3) 2 -C 6 H 4 -O- , or ^{-COO-Y 1} -OCO- ^{(Y 1} is _- shows a _{(CH 2) l - - (} l = 1~20) or _{-H 2 C-HC (-O-} C (= O) -CH 3) -CH 2.) the Represents.)

3. Item 2. The polyimide adhesive according to Item 1 or 2, wherein the ratio of the moles of the component (a1) to the moles of the component (a2) is 1 <[(a1) / (a2)] <1.2.

4. Item 5. The polyimide adhesive according to any one of Items 1 to 3, wherein the monomer group (α) further contains a diaminopolysiloxane (a3).

5. The ratio of the moles of the component (a1) to the total moles of the components (a2) and (a3) is 1 <[(a1) / [(a2) + (a3)]] <1.2. Item 4. A polyimide-based adhesive.

6. The ratio of the moles of the component (a2) to the total moles of the components (a2) and (a3) is 0.3 <[(a2) / [(a2) + (a3)]] <1. Item 4. A polyimide adhesive according to item 4 or 5.

7. The component (A2) is represented by the general formula: X ² —NH ₂ (wherein, X ² represents a linear, branched or cyclic alkyl group having 1 to 22 carbon atoms, or an aromatic group). The polyimide adhesive according to any one of items 1 to 6, which is a primary monoamine.

8. The polyimide adhesive according to any one of items 1 to 7, wherein the amount of the component (A2) used is 0.8 to 1.2 mol per 1 mol of the terminal acid anhydride group of the component (A1).

9. (2) The polyimide adhesive according to any one of Items 1 to 8, wherein the component (2) contains at least one selected from the group consisting of epoxy compounds, benzoxazine compounds, bismaleimide compounds and cyanate ester compounds.

（式中、Ｚはフェニレン基又はシクロヘキセニル基を表す。） 10. Item 10. The polyimide-based adhesive according to Item 9, wherein the epoxy compound contains tetraglycidyl xylene diamine having the following structure.

(In the formula, Z represents a phenylene group or a cyclohexenyl group.)

11. Any one of the above items 1 to 10, wherein the component (2) is 11 to 900 parts by weight and the component (3) is 150 to 900 parts by weight with respect to 100 parts by weight of the component (1) (as calculated as solid content). Polyimide adhesive.

12. A film-like adhesive comprising the polyimide adhesive according to any one of Items 1 to 11.

13. An adhesive layer comprising the polyimide adhesive according to any one of Items 1 to 11 or the film-like adhesive material according to Item 12.

14. An adhesive sheet comprising the adhesive layer of item 13 and a support film as constituent elements.

15. A resin-coated copper foil comprising the adhesive layer of item 13 and a copper foil as components.

16. A copper clad laminate comprising the resin-coated copper foil and the copper foil of item 15 as constituent elements.

17. A copper-clad laminate comprising the resin-coated copper foil of item 15 and one insulating sheet as constituent elements.

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.

19. One printed wiring board or one printed circuit board which is a core substrate,
The adhesive layer of item 13 above,
One printed wiring board or one printed circuit board which is another base material,
Including as a component,
Multilayer wiring board.

20. A method for manufacturing a multilayer wiring board, which includes the following steps 1 and 2.
Step 1: Bringing the polyimide adhesive according to any one of the above items 1 to 11 or the film adhesive according to the above item 12 to at least one surface of one printed wiring board or one printed circuit board which is a core substrate. According to the process for producing a substrate with an adhesive layer, the process 2: a process for laminating one printed wiring board or one printed circuit board on the substrate with an adhesive layer and crimping under heating and pressure.

  The polyimide-based adhesive of the present invention has a low loss elastic modulus at the B stage and exhibits appropriate fluidity, and therefore wets the adherend such as a printed wiring board and a printed circuit board.

  The polyimide film adhesive of the present invention also has a low loss elastic modulus in the B stage and exhibits appropriate fluidity, and therefore adheres well to an adherend such as a printed wiring board and a printed circuit board.

  The adhesive layer of the present invention is obtained from the above-mentioned polyimide-based adhesive or polyimide-based film-like adhesive, and shows good heat resistance and low dielectric properties after post-curing while showing appropriate fluidity in the B stage. Show. Hereinafter, the adhesive layer may be simply referred to as “adhesive layer”.

  The polyimide-based adhesive and the polyimide-based film-shaped adhesive of the present invention, and an adhesive sheet obtained by using them, a resin-coated copper foil, a copper-clad laminate and a printed wiring board are materials for a multilayer wiring board excellent in low dielectric properties. Is useful as In addition, the members obtained using them are mobile communication devices typified by smartphones and mobile phones, their base station devices, network-related electronic devices such as servers and routers, and members of products that handle high-frequency signals such as large computers. Is useful as

6 is a graph showing changes in loss modulus (G ″) of the polyimide-based adhesives of Example 3 and Comparative Example 2.

  The polyimide-based adhesive of the present invention is obtained by converting the terminal acid anhydride group of a predetermined acid anhydride group-terminated polyimide (A1) (hereinafter, also referred to as (A1) component) to a primary monoamine (A2) (hereinafter, (A2)). Modified polyimide (1) (hereinafter, also referred to as (1) component) sealed with a component, a cross-linking agent (2) (hereinafter, also referred to as (2) component), and an organic solvent ( 3) (hereinafter, also referred to as the component (3)).

  The component (A1) is a monomer group (α) containing an aromatic tetracarboxylic acid anhydride (a1) (hereinafter, also referred to as the component (a1)) and a dimer diamine (a2) (hereinafter, also referred to as the component (a2)). ) (Hereinafter, also referred to as component (α)).

  As the component (a1), various known aromatic tetracarboxylic acid anhydrides can be used. Specifically, for example, those shown by the following structures can be mentioned.

（式中、Ｙは単結合、−ＳＯ_２−、−ＣＯ−、−Ｏ−、−Ｏ−Ｃ_６Ｈ_４−Ｃ（ＣＨ_３）_２−Ｃ_６Ｈ_４−Ｏ−又は−ＣＯＯ−Ｙ^１−ＯＣＯ−（Ｙ^１は−（ＣＨ_２）_ｌ−（ｌ＝１〜２０）若しくは−Ｈ_２Ｃ−ＨＣ（−Ｏ−Ｃ（＝Ｏ）−ＣＨ_３）−ＣＨ_２−を示す。）を表す。）

(Wherein, Y represents a single _{bond, -SO 2 -, - CO -} , - O -, - O-C 6 H 4 -C (CH 3) 2 -C 6 H 4 -O- , or ^{-COO-Y 1} -OCO- ^{(Y 1} is _- shows a _{(CH 2) l - - (} l = 1~20) or _{-H 2 C-HC (-O-} C (= O) -CH 3) -CH 2.) the Represents.)

  Specific examples of the component (a1) include, for example, pyromellitic dianhydride, 4,4′-oxydiphthalic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, and 3, 3 ', 4,4'-diphenyl ether tetracarboxylic acid dianhydride, 3,3', 4,4'-diphenyl sulfone tetracarboxylic acid dianhydride, 1,2,3,4-benzenetetracarboxylic acid anhydride, 1,4,5,8-naphthalene tetracarboxylic acid anhydride, 2,3,6,7-naphthalene tetracarboxylic acid anhydride, 3,3 ′, 4,4′-biphenyl tetracarboxylic acid dianhydride, 2, 2 ', 3,3'-biphenyltetracarboxylic dianhydride, 2,3,3', 4'-biphenyltetracarboxylic dianhydride, 2,3,3 ', 4'-benzophenonetetracarboxylic dianhydride Thing 2, , 3 ', 4'-Diphenyl ether tetracarboxylic acid dianhydride, 2,3,3', 4'-diphenyl sulfone tetracarboxylic acid dianhydride, 2,2-bis (3,3 ', 4,4'- Tetracarboxyphenyl) tetrafluoropropane dianhydride, 2,2′-bis (3,4-dicarboxyphenoxyphenyl) sulfone dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride , 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, cyclopentanetetracarboxylic acid anhydride, butane-1,2,3,4-tetracarboxylic acid, 2,3,5-tricarboxy Examples include cyclopentyl acetic anhydride and 4,4 ′-[propane-2,2-diylbis (1,4-phenyleneoxy)] diphthalic dianhydride, and combinations of two or more thereof. May be. Among them, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 4,4 ′-[propane-2,2-diylbis (1 , 4-phenyleneoxy)] diphthalic dianhydride, and at least one selected from the group consisting of 4,4′-oxydiphthalic anhydride.

  The dimer diamine as the component (a2) is a compound derived from dimer acid that is a dimer of unsaturated fatty acid such as oleic acid (see JP-A-9-12712, etc.), and various known dimer diamines are used. It can be used without particular limitation.

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

  Examples of commercially available products of the component (a2) include Versamine 551 (manufactured by BASF Japan Ltd.), Versamine 552 (manufactured by Cognix Japan Ltd .; hydrogenated product of Versamine 551), PRIAMINE 1075, PRIAMINE 1074 (all are Croda Japan ( Co., Ltd.) and the like, and two or more types can be combined.

  The amounts of the component (a1) and the component (a2) used are not particularly limited, but from the viewpoint of achieving a low loss elastic modulus of the adhesive layer, a heat-resistant adhesive property, and a low dielectric property, the amount of the component (a1) and the component (a1) are usually The molar ratio of the component a2) is 1 <[(a1) / (a2)] <1.2, preferably 1.05 ≦ [(a1) / (a2)] ≦ 1.15. I wish I had it. When the ratio is more than 1, the heat-resistant adhesive property of the adhesive layer tends to be good, and when it is less than 1.2, the loss loss elastic modulus of the adhesive layer can be made low, and its low dielectric property is obtained. Also tends to be good.

  The component (α) may include the diaminopolysiloxane (a3) (hereinafter, also referred to as the component (a3)). The loss elastic modulus of the adhesive layer can be lowered by the component (a3), and its heat resistant adhesiveness can be improved.

  Various known diaminopolysiloxanes can be used as the component (a3). Specifically, for example, α, ω-bis (2-aminoethyl) polydimethylsiloxane, α, ω-bis (3-aminopropyl) polydimethylsiloxane, α, ω-bis (4-aminobutyl) polydimethyl Siloxane, α, ω-bis (5-aminopentyl) polydimethylsiloxane, α, ω-bis [3- (2-aminophenyl) propyl] polydimethylsiloxane, α, ω-bis [3- (4-aminophenyl) ) Propyl] polydimethylsiloxane and the like, and two or more kinds may be combined.

  The amounts of the component (a1), the component (a2) and the component (a3) are not particularly limited, but in general, the component (a1) is usually used from the viewpoint of achieving a low loss elastic modulus of the adhesive layer, a balance between heat resistant adhesive properties and low dielectric properties. The ratio of the moles of the components to the total moles of the components (a2) and (a3) is 1 <[(a1) / [(a2) + (a3)]] <1.2, preferably It may be in the range of about 1.05 ≦ [(a2) / [(a2) + (a3)]] ≦ 1.15. When the ratio is more than 1, the heat-resistant adhesive property of the adhesive layer tends to be good, and when it is less than 1.2, the loss loss elastic modulus of the adhesive layer can be made low, and its low dielectric property is obtained. Also tends to be good.

  The use ratio of the component (a2) and the component (a3) is not particularly limited, but from the viewpoint of achieving a low loss elastic modulus of the adhesive layer, a balance between heat-resistant adhesive properties and low dielectric properties, usually, the moles of the component (a2): The ratio of the total moles of the component (a2) and the component (a3) is 0.3 <[(a2) / [(a2) + (a3)]] <1, preferably 0.5 ≦ [(a2 ) / [(A2) + (a3)]] ≦ 1. When the ratio is larger than 0.3, the heat-resistant adhesiveness of the adhesive layer tends to be good, and when it is smaller than 1, it is possible to reduce the loss elastic modulus of the adhesive layer, and its low dielectric property. Also tends to be good.

  The component (α) may include a diamine component (hereinafter, also referred to as a component (a4)) other than the components (a2) and (a3), if necessary. Specific examples of the component (a4) include diaminocyclohexane, diaminodicyclohexylmethane, dimethyl-diaminodicyclohexylmethane, tetramethyl-diaminodicyclohexylmethane, diaminodicyclohexylpropane, diaminobicyclo [2.2.1] heptane and bis. (Aminomethyl) -bicyclo [2.2.1] heptane, 3 (4), 8 (9) -bis (aminomethyl) tricyclo [5.2.1.02,6] decane, 1,3-bisamino Alicyclic diamines such as methylcyclohexane and isophoronediamine; bis such as 2,2-bis [4- (3-aminophenoxy) phenyl] propane and 2,2-bis [4- (4-aminophenoxy) phenyl] propane Aminophenoxyphenylpropanes; 3,3'-diaminodipheni Diaminodiphenyl ethers such as ether, 3,4′-diaminodiphenyl ether and 4,4′-diaminodiphenyl ether; phenylenediamines such as p-phenylenediamine and m-phenylenediamine; 3,3′-diaminodiphenyl sulfide, 3,4 Diaminodiphenyl sulfides such as'-diaminodiphenyl sulfide and 4,4'-diaminodiphenyl sulfide; Diamino such as 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone and 4,4'-diaminodiphenyl sulfone Diphenyl sulfones; 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone and other diaminobenzophenones; 3,3'-diaminodiphenylmethane, 4,4 ' Diaminodiphenylmethanes such as diaminodiphenylmethane and 3,4′-diaminodiphenylmethane; 2,2-di (3-aminophenyl) propane, 2,2-di (4-aminophenyl) propane, 2- (3-aminophenyl) Diaminophenylpropanes such as 2- (4-aminophenyl) propane; 2,2-di (3-aminophenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-di (4-Aminophenyl) -1,1,1,3,3,3-hexafluoropropane, 2- (3-aminophenyl) -2- (4-aminophenyl) -1,1,1,3,3 , 3-hexafluoropropane and other diaminophenylhexafluoropropanes; 1,1-di (3-aminophenyl) -1-phenylethane, 1,1-di (4-aminophenyl) ) -1-phenylethane, 1- (3-aminophenyl) -1- (4-aminophenyl) -1-phenylethane and other diaminophenylphenylethanes; 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 bisaminophenoxybenzenes; 1,3- Bis such as bis (3-aminobenzoyl) benzene, 1,3-bis (4-aminobenzoyl) benzene, 1,4-bis (3-aminobenzoyl) benzene, 1,4-bis (4-aminobenzoyl) benzene Aminobenzoylbenzenes; 1,3-bis (3-amino-α, α-dimethylbenzyl) benzene, 1,3-bis (4-amino-α, α- Bisaminodimethylbenzenes such as dimethylbenzyl) benzene, 1,4-bis (3-amino-α, α-dimethylbenzyl) benzene and 1,4-bis (4-amino-α, α-dimethylbenzyl) benzene; 1,3-bis (3-amino-α, α-ditrifluoromethylbenzyl) benzene, 1,3-bis (4-amino-α, α-ditrifluoromethylbenzyl) benzene, 1,4-bis (3- Bisaminoditrifluoromethylbenzylbenzenes such as amino-α, α-ditrifluoromethylbenzyl) benzene and 1,4-bis (4-amino-α, α-ditrifluoromethylbenzyl) benzene; 2,6-bis ( 3-aminophenoxy) benzonitrile, 2,6-bis (3-aminophenoxy) pyridine, 4,4'-bis (3-aminophenoxy) biphe And aminophenoxybiphenyls such as 4,4′-bis (4-aminophenoxy) biphenyl; bis [4- (3-aminophenoxy) phenyl] ketone, bis [4- (4-aminophenoxy) phenyl] ketone, etc. Aminophenoxyphenyl ketones; bis [4- (3-aminophenoxy) phenyl] sulfide, bis [4- (4-aminophenoxy) phenyl] sulfide, and other aminophenoxyphenyl sulfides; bis [4- (3-amino Aminophenoxyphenyl sulfones such as phenoxy) phenyl] sulfone and bis [4- (4-aminophenoxy) phenyl] sulfone; 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; 1,3-bis [4- (3-aminophenoxy) benzoyl] benzene, 1,3-bis [4- (4-aminophenoxy) benzoyl] benzene, 1,4-bis [4- (3-aminophenoxy) benzoyl] benzene, 1 , 4-bis [4- (4-aminophenoxy) benzoyl] benzene, 1,3-bis [4- (3-aminophenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [ -(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) benzoyl] diphenyl ether, 4,4′-bis [4- (4-amino-α, α-Dimethylbenzyl) phenoxy] benzophenone, 4,4′-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] diphenylsulfone, 4,4′-bis [4- (4-aminophenoxy) Phenoxy] diphenyl sulfone, 3,3′-diamino-4,4′-diphenoxybenzophenone, 3,3′-diamino-4,4′-dibiphenoxybenzophenone 3,3'-diamino-4-phenoxybenzophenone, 3,3'-diamino-4-biphenoxybenzophenone, 6,6'-bis (3-aminophenoxy) 3,3,3, '3'-tetramethyl -1,1'-spirobiindane 6,6'-bis (4-aminophenoxy) 3,3,3, '3'-tetramethyl-1,1'-spirobiindane, 1,3-bis (3-aminopropyl ) Tetramethyldisiloxane, 1,3-bis (4-aminobutyl) tetramethyldisiloxane, bis (aminomethyl) ether, bis (2-aminoethyl) ether, bis (3-aminopropyl) ether, bis (2 -Aminomethoxy) ethyl] ether, bis [2- (2-aminoethoxy) ethyl] ether, bis [2- (3-aminoprotoxy) 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-diamino Decane, 1,11-diaminoundecane, 1,12-diaminododecane, etc. are mentioned, and two or more kinds are combined. May be combined. The amount of the component (a4) used is not particularly limited, but is usually less than 75 mol% when the total diamine component is 100 mol%.

  The component (A1) can be produced by various known methods. For example, the components (a1) and (a2) and, if necessary, the components (a3) and / or (a4) are usually added at a temperature of about 60 to 120 ° C. (preferably 80 to 100 ° C.). Polyamide is obtained by polyaddition reaction for about 1 to 2 hours (preferably 0.1 to 0.5 hours). Then, the polyamide is further imidized, that is, dehydrated and ring-closed at a temperature of about 80 to 250 ° C. (preferably 100 to 200 ° C.) for about 0.5 to 50 hours (preferably 1 to 20 hours). Good.

  Various known reaction catalysts, dehydrating agents, and the component (3) described later can be used in the poly (negative addition) reaction and the imidization reaction. 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. The above may be combined. Examples of the dehydrating agent include aliphatic acid anhydrides such as acetic anhydride, aromatic acid anhydrides such as benzoic anhydride, and the like, and two or more kinds may be combined. As the component (3), an aprotic polar solvent is preferable, and cyclohexanone and methylcyclohexane are particularly preferable.

  The imide ring closure rate of the component (A1) is not particularly limited, but is usually 70% or more, preferably 85 to 100%. "Imide ring closure rate" means the content of cyclic imide bonds (the same applies hereinafter), and can be determined by various spectroscopic means such as NMR or IR analysis.

  The number average molecular weight of the component (A1) (referred to as a polystyrene conversion value by gel permeation chromatography. The same applies hereinafter) is not particularly limited, but is usually about 4000 to 19000, preferably about 6500 to 14000. If the number average molecular weight is more than 4000, the heat-resistant adhesiveness of the adhesive layer tends to be good, and if it is less than 19000, the loss loss elastic modulus of the adhesive layer can be made low and its low dielectric property is also low. It tends to be good.

  Other physical properties of the component (A1) include a softening point. The softening point is a measured value obtained by using a commercially available measuring device (“ARES-2KSTD-FCO-STD”, manufactured by Rheometric Scientfic). Specifically, in the viscoelastic profile of the component (A1), the temperature at which the rigidity starts to decrease is regarded as the softening point. The value of the softening point is not particularly limited, but is usually about 20 to 200 ° C, preferably about 50 to 120 ° C. When the glass transition temperature is higher than 20 ° C., the heat-resistant adhesiveness of the adhesive layer tends to be good, and when it is lower than 200 ° C., the loss loss elastic modulus of the adhesive layer can be lowered, and the low dielectric constant The characteristics tend to be good.

  The terminal acid anhydride group concentration of the component (A1) is not particularly limited, but is usually about 2500 to 20000 eq / g, preferably about 3000 to 10000 eq / g.

The component (A2) is a primary monoamine represented by the general formula: X ¹ —NH ₂ (wherein, X ¹ represents a hydrocarbon group having 1 to 22 carbon atoms), and by using this, adhesion is achieved. It is possible to improve the fluidity of the layer while maintaining its heat resistant adhesion and low dielectric properties.

  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 have the alkyl group and / or the alkenyl group as a substituent.

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

（式中、Ｘ^１は炭素数１〜２２の炭化水素基を示す。）

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

The component (A2) is represented by the general formula: X ² —NH ₂ (wherein, X ² represents a linear, branched or cyclic alkyl group having 1 to 22 carbon atoms, or an aromatic group). Preferred are primary monoamines. The amine forms the terminal structure of the component (1) by reacting with the terminal acid anhydride group of the component (A1).

（式中、式中、Ｘ^２は炭素数１〜２２の直鎖状、分岐状若しくは環状のアルキル基、又は芳香族基を示す。）

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

  Specific examples of the primary monoamine include ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, pentylamine, isopentylamine, tert-pentylamine, Primary alkyl monoamines such as n-octylamine, n-decylamine, n-isodecylamine, n-tridecylamine, n-laurylamine, n-cetylamine and n-stearylamine, and aniline, phenoxyaniline and methylaniline. Examples include primary aryl monoamines, and these may be a combination of two or more kinds. For example, when the primary alkyl monoamine is of animal or plant origin, it may be a mixture of a plurality of primary alkyl monoamines having different carbon numbers. Also, a mixture in which a primary monoamine and a primary arylamine are combined as such a mixture can be used. Among the primary amines, the alkyl group has about 4 to 22 carbon atoms (preferably 10 to 20 carbon atoms) in that the loss elastic modulus can be lowered while maintaining the heat resistant adhesiveness and low dielectric properties of the adhesive layer. At least one selected from the group consisting of primary alkyl monoamines and primary aryl monoamines (about 20) is preferable. Particularly, the primary aryl monoamine tends to contribute to the compatibility (transparency) of the adhesive layer according to the present invention. Examples of commercial products of the primary alkyl monoamines include lipomin CD (coconut alkylamine), lipomin OD (oleylamine), lipomin TD (beef tallow alkylamine), lipomin 8D (octylamine), lipomin 12D (dodecylamine), lipomin 18D. (Octadecylamine), pharmin CS (coconut amine), pharmin 08D (caprylamine), pharmin 20D (laurylamine), pharmin 80 (stearylamine), pharmin 86T (stearylamine), pharmin T (beef tallow amine) and the like. .

  The amount of the component (A2) used is not particularly limited, but usually 1 mol of the terminal acid anhydride group of the component (A1) is used from the viewpoint of achieving a low loss elastic modulus of the adhesive layer, heat resistant adhesion and a balance of low dielectric properties. On the other hand, the amount of the component (A2) is about 0.8 to 1.2 mol, preferably about 0.9 to 1.1 mol.

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

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

  The number average molecular weight of the component (1) is not particularly limited, but is usually about 5,000 to 20,000, preferably about 7,500 to 15,000. When the number average molecular weight is more than 5,000, the heat-resistant adhesiveness of the adhesive layer tends to be good, and when it is less than 20,000, the loss loss elastic modulus of the adhesive layer can be made low and its low dielectric property is also low. It tends to be good.

  The value of the softening point of the component (1) is not particularly limited, but is usually about 20 to 200 ° C, preferably about 50 ° C to 120 ° C. When the glass transition temperature is higher than 20 ° C., the heat-resistant adhesiveness of the adhesive layer tends to be good, and when it is lower than 200 ° C., the loss loss elastic modulus of the adhesive layer can be lowered, and the low dielectric constant The characteristics tend to be good.

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

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

  Examples of the epoxy compound include a phenol novolac type epoxy compound, a cresol novolac type epoxy compound, a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, a bisphenol S type epoxy compound, a hydrogenated bisphenol A type epoxy compound, and a hydrogenated bisphenol F type. Epoxy compound, stilbene type epoxy compound, triazine skeleton containing epoxy compound, fluorene skeleton containing epoxy compound, linear aliphatic epoxy compound, alicyclic epoxy compound, glycidyl amine type epoxy compound, triphenolphenol methane type epoxy compound, alkyl modified Triphenolmethane type epoxy compound, biphenyl type epoxy compound, dicyclopentadiene skeleton-containing epoxy compound, naphthalene skeleton-containing epoxy compound , Aryl alkylene type epoxy compounds, tetraglycidyl xylylenediamine, modified epoxy compound comprising modified with these epoxy compounds dimer acid, and dimer acid diglycidyl ester and the like, may be in combination of two or more. Examples of commercially available products include "jER828", "jER834", "jER807" manufactured by Mitsubishi Chemical Co., Ltd., "ST-3000" manufactured by Nippon Steel Chemical Co., Ltd., and manufactured by Daicel Chemical Industries, Ltd. "Celoxide 2021P", Nippon Steel Chemical Co., Ltd. "YD-172-X75", Mitsubishi Gas Chemical Co., Ltd. "TETRAD-X", etc. are mentioned. Among these, from the viewpoint of the balance of heat-resistant adhesiveness, moisture-absorptive solder heat resistance and low dielectric properties, a group consisting of a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, a hydrogenated bisphenol A type epoxy compound and an alicyclic epoxy compound is selected. At least one selected is preferable.

  Particularly, tetraglycidyl xylylenediamine having the following structure has good compatibility with the component (1). Further, when this is used, it is easy to reduce the loss elastic modulus of the adhesive layer, and the heat-resistant adhesive property and low dielectric property are also improved.

（式中、Ｚはフェニレン基又はシクロヘキセニル基を表す。）

(In the formula, Z represents a phenylene group or a cyclohexenyl group.)

  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, 4-methyl-hexahydrophthalic anhydride. Acid or a mixture of 4-methyl-hexahydrophthalic anhydride and hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyl-tetrahydrophthalic anhydride, nadic acid anhydride, methylnadic acid anhydride, norbornane-2,3-dicarboxylic acid anhydride Acid anhydride hardeners such as methyl norbornane-2,3-dicarboxylic acid anhydride, methylcyclohexene dicarboxylic acid anhydride, 3-dodecenyl succinic anhydride, octenyl succinic anhydride; dicyandiamide (DICY), aromatic diamine ( Product name "LonzatureM- EA "," Lonzacure M-DETDA ", etc., all manufactured by Lonza Japan Co., Ltd., amine-based curing agents such as aliphatic amines; phenol novolac resins, cresol novolac resins, bisphenol A type novolac resins, triazine modified phenol novolac resins, Phenolic hydroxyl group-containing phosphazene (trade name "SPH-100" manufactured by Otsuka Chemical Co., Ltd.) and other phenolic curing agents, cyclic phosphazene compounds, maleic acid-modified rosin and its hydrides and other rosin crosslinking agents And two or more kinds may be combined. Among these, a phenol-based curing agent, particularly a phenolic hydroxyl group-containing phosphazene-based curing agent is preferable. The amount of these curing agents used is not particularly limited, but is usually about 0.1 to 120% by weight, preferably about 10 to 40% by weight, when the solid content of the adhesive of the present invention is 100% by weight. is there.

  When an epoxy compound is used as the component (2) and the curing agent is used, a reaction catalyst can be used. Specifically, for example, three compounds such as 1,8-diaza-bicyclo [5.4.0] undecene-7, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol, etc. Secondary amines; 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole and other imidazoles; tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, phenyl Organic phosphines such as phosphine; tetraphenyls such as tetraphenylphosphonium / tetraphenylborate, 2-ethyl-4-methylimidazole / tetraphenylborate, N-methylmorpholine / tetraphenylborate Niruboron salts and the like, may be in combination of two or more. The amount of the reaction catalyst used is not particularly limited, but is usually about 0.01 to 5% by weight when the solid content of the adhesive of the present invention is 100% by weight.

  Examples of the benzoxazine compound include 6,6- (1-methylethylidene) bis (3,4-dihydro-3-phenyl-2H-1,3-benzoxazine) and 6,6- (1-methylethylidene). ) Bis (3,4-dihydro-3-methyl-2H-1,3-benzoxazine) and the like, and two or more kinds may be combined. In addition, a phenyl group, a methyl group, a cyclohexyl group or the like may be bonded to the nitrogen of the oxazine ring. Examples of commercially available products include "benzoxazine Fa type" and "benzoxazine Pd type" manufactured by Shikoku Chemicals Co., Ltd., "RLV-100" manufactured by Air Water Co., Ltd., and the like. Is mentioned.

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

  Examples of the cyanate ester compound include 2-allylphenol cyanate ester, 4-methoxyphenol cyanate ester, 2,2-bis (4-cyanatophenol) -1,1,1,3,3,3-hexafluoro. Propane, bisphenol A cyanate ester, diallyl bisphenol A cyanate ester, 4-phenylphenol cyanate ester, 1,1,1-tris (4-cyanatophenyl) ethane, 4-cumylphenol cyanate ester, 1,1-bis ( 4-cyanatophenyl) ethane, 4,4′-bisphenol cyanate ester, 2,2-bis (4-cyanatophenyl) propane and the like are mentioned, and two or more kinds may be combined. Moreover, as a commercial item, "PRIMASET BTP-6020S (made by Lonza Japan Co., Ltd.)" etc. are mentioned, for example.

  As the component (3), various known solvents can be used without particular limitation. Specific examples include aprotic polar solvents such as N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, dimethylsulfoxide, N-methylcaprolactam, methyltriglyme, and methyldiglyme, cyclohexanone, and methylcyclohexane. Alicyclic solvents, alcohol-based solvents such as methanol, ethanol, propanol, benzyl alcohol and cresol, aromatic solvents such as toluene and the like, and two or more kinds may be combined.

  In the adhesive of the present invention, if necessary, the ring-opening esterification reaction catalyst or dehydrating agent, plasticizer, weathering agent, antioxidant, heat stabilizer, lubricant, antistatic agent, brightener, colorant, Additives such as a conductive agent, a release agent, a surface treatment agent, a viscosity modifier, a phosphorus-based flame retardant, a flame retardant filler, a silica filler, and a fluorine filler can be added.

  The amounts of the component (1), the component (2) and the component (3) are not particularly limited, but from the viewpoint of the low loss elastic modulus of the adhesive layer, the heat resistant adhesiveness and the low dielectric property balance, the component (1) 100 It is preferable that the component (2) is 11 to 900 parts by weight and the component (3) is 150 to 900 parts by weight with respect to parts by weight.

  The film adhesive of the present invention is an article made of the polyimide adhesive of the present invention. Specifically, for example, the adhesive is applied to an appropriate support, heated, and then cured by evaporating the component (3), and then peeled from the support. The thickness of the adhesive is not particularly limited, but is usually about 3 to 40 μm. Examples of the support include the following.

  The adhesive sheet of the present invention is an article that includes an adhesive layer made of the polyimide adhesive of the present invention or the film adhesive of the present invention and a support film as constituent elements. Examples of the support include polyester, polyimide, polyimide-silica hybrid, polyethylene, polypropylene, polyethylene terephthalate, polyethylene naphthalate, polymethyl methacrylate resin, polystyrene resin, polycarbonate resin, acrylonitrile-butadiene-styrene resin, and ethylene terephthalate. Examples thereof include plastic films such as aromatic polyester resins (so-called liquid crystal polymers; manufactured by Kuraray Co., Ltd., “Bexter”) obtained from phenol, phthalic acid, hydroxynaphthoic acid and the like and parahydroxybenzoic acid. Further, when applying the polyimide-based adhesive according to the present invention to the support, the coating means can be adopted. The thickness of the coating layer is also not particularly limited, but it may be in the range where the thickness after drying is usually about 1 to 100 μm, preferably about 3 to 50 μm. The adhesive layer of the adhesive sheet may be protected with various protective films.

  The resin-coated copper foil of the present invention is an article including the adhesive layer of the present invention and the copper foil as constituent elements. Specifically, the polyimide-based adhesive or the film-shaped adhesive is applied or bonded to a copper foil. Examples of the copper foil include rolled copper foil and electrolytic copper foil. The thickness is not particularly limited and is usually about 1 to 100 μm, preferably about 2 to 38 μm. The copper foil may be subjected to various surface treatments (roughening, rust prevention, etc.). Examples of the rustproofing treatment include so-called mirror-finishing treatment such as plating treatment using a plating solution containing Ni, Zn, Sn and the like, and chromate treatment. The coating method may be the above-mentioned method. Further, the adhesive layer of the resin-coated copper foil may be uncured, or may be partially cured or completely cured under heating. The partially cured adhesive layer is in a so-called B stage. The thickness of the adhesive layer is also not particularly limited and is usually about 0.5 to 30 μm. Further, a double-sided resin-coated copper foil can be obtained by further bonding a copper foil to the adhesive surface of the resin-coated copper foil.

  The copper clad laminate of the present invention is an article obtained by laminating the resin-coated copper foil of the present invention and a copper foil or an insulating sheet, and is also called CCL (Copper Clad Laminate). Specifically, the resin-coated copper foil of the present invention is pressure-bonded to at least one surface or both surfaces of various known copper foils or insulating sheets under heating. When it is attached to one surface, a different material from the resin-coated copper foil of the present invention may be pressure-bonded to the other surface. The number of resin-coated copper foils and insulating sheets in the copper-clad laminate is not particularly limited. A prepreg is preferable as the insulating sheet. The prepreg refers to a sheet-shaped material obtained by impregnating a reinforcing material such as glass cloth with a resin and curing it to the B stage (JIS C 5603). As the resin, an insulating resin such as a polyimide resin, a phenol resin, an epoxy resin, a polyester resin, a liquid crystal polymer or an aramid resin is usually used. The thickness of the prepreg is not particularly limited and is usually about 20 to 500 μm. The heating / pressure bonding conditions are not particularly limited, and are usually 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 obtained by forming a circuit pattern on the copper foil surface of the copper clad laminate of the present invention. Examples of patterning means include a subtractive method and a semi-additive method. Examples of the semi-additive method include a method of patterning a copper foil surface of the copper clad laminate of the present invention with a resist film, electrolytic copper plating, removing the resist, and etching with an alkaline solution. Moreover, the thickness of the circuit pattern layer in the printed wiring board is not particularly limited. A multilayer substrate can also be obtained by using the printed wiring board as a core substrate and laminating the same printed wiring board or another known printed wiring board or printed circuit board on the core substrate. At the time of lamination, not only the polyimide adhesive of the present invention but also other known polyimide adhesives can be used. Further, the number of stacked layers in the multilayer substrate is not particularly limited. Further, via holes may be inserted and plated inside each time the layers are laminated. The line / space ratio of the circuit pattern is not particularly limited, but is usually about 1 μm / 1 μm to 100 μm / 100 μm. The height of the circuit pattern is not particularly limited, but is usually about 1 to 50 μm.

  The multilayer wiring board according to the present invention includes one printed wiring board or one printed circuit board which is a core base material, an adhesive layer according to the present invention, and one printed wiring board or one print which is another base material. An article including a circuit board as a constituent element. Such one printed wiring board or one printed circuit board may be those according to the present invention, or may be various known ones.

The multilayer wiring board according to the present invention can be obtained by a manufacturing method including the following steps 1 and 2.
Step 1: A polyimide-based adhesive or a film-like adhesive according to the present invention is brought into contact with at least one side of one printed wiring board or one printed circuit board which is a core substrate to produce a substrate with an adhesive layer. Step 2: Step of laminating one printed wiring board or one printed circuit board on the base material with the adhesive layer, and crimping under heat and pressure

  Such one printed wiring board or one printed circuit board may be those according to the present invention, or may be various known ones.

  In step 1, the means for bringing the polyimide-based adhesive or the film adhesive of the present invention into contact with the adherend is not particularly limited, and various known coating means, for example, a curtain coater, a roll coater, a laminator, a press or the like may be used. Can be used.

  The heating temperature and pressure bonding time in step 2 are not particularly limited, but usually (a) after contacting the polyimide-based adhesive or the film-shaped adhesive of the present invention with at least one surface of the core substrate, it is usually about 70 to 200 ° C. After heating for about 1 to 10 minutes to perform a curing reaction, heat treatment is usually further performed at about 150 ° C to 250 ° C for about 10 minutes to 3 hours in order to advance the curing reaction of the component (2) (2). Good to do. Although the pressure is not particularly limited, it is usually about 0.5 to 20 MPa, preferably about 1 to 8 MPa throughout the steps (a) and (a).

Hereinafter, the present invention will be specifically described with reference to Examples , Comparative Examples and Reference Examples , but the scope of the present invention is not limited thereby. In addition, in each example, parts and% are based on weight unless otherwise specified. The number average molecular weight is a value obtained by using a commercially available measuring device (“HLC-8220GPC”, manufactured by Tosoh Corporation), and the glass transition temperature is a commercially available measuring device (“DSC6200”, It is a value obtained by using Seiko Instruments Inc.).

<Synthesis of acid anhydride group-terminated polyimide>
Production example 1
3,3 ', 4,4'-benzophenone tetracarboxylic acid dianhydride (trade name "BTDA-PF", Evonik Japan Co., Ltd.) was placed in a reaction vessel equipped with a stirrer, a water separator, a thermometer and a nitrogen gas introduction tube. )) 225.00 g, cyclohexanone 1046.25 g, and methylcyclohexane 209.25 g were charged and heated to 60 ° C. Next, 345.93 g of dimer diamine (trade name "PRIAMINE1075", manufactured by Croda Japan Co., Ltd.) was added, and the acid anhydride group-terminated polyimide (A1-1) was subjected to an imidization reaction at 130 ° C for 12 hours. (Hereinafter, also referred to as component (A1-1).) A solution (nonvolatile content 31.0%) was obtained. The acid component / amine component molar ratio of the component (A1-1) was 1.08, the number average molecular weight was 8500, and the softening point was 70 ° C.

Production example 2
755.63 g of the solution of the component (A1-1) was put in the same reaction vessel as in Production Example 1, and the solvent was distilled off under reduced pressure until the nonvolatile content became 34.4%. Then, 2.76 g of octylamine (trade name “Lipomin 8D”, manufactured by Lion Specialty Chemicals Co., Ltd.) was further charged as the component (A2), and reacted at 140 ° C. for 16 hours to obtain the end-capped polyimide (1-1). ) (Hereinafter, also referred to as component (1-1)) to obtain a solution (nonvolatile content: 35.9%). The acid anhydride terminal group / octylamine molar ratio of the component (A1-1) was 1.0, the number average molecular weight was 10,000, and the softening point was 70 ° C.

Production Example 3
755.63 g of the solution of the component (A1-1) was placed in the same reaction vessel as in Production Example 1, and the solvent was distilled off under reduced pressure until the nonvolatile content became 34.0%. Then, as component (A2), 4.69 g of coconut amine (trade name "Farmin CS", manufactured by Kao Corporation, main alkyl composition C12: 51%, C14: 19%, C16: 8% C18: 6%) is further added. By charging and reacting at 140 ° C. for 16 hours, a solution (nonvolatile content: 35.2%) of end-capped polyimide (1-2) (hereinafter, also referred to as (1-2) component) was obtained. The acid anhydride terminal group / octylamine molar ratio of the component (A1-1) was 1.0, the number average molecular weight was 10500, and the softening point was 70 ° C.

Production Example 4
755.63 g of the solution of the component (A1-1) was put in the same reaction vessel as in Production Example 1, and the solvent was distilled off under reduced pressure until the nonvolatile content became 34.2%. Then, 1.99 g of aniline (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was further charged as the component (A2) and reacted at 140 ° C. for 16 hours to obtain an end-capped polyimide (1-3) (hereinafter (1- A solution (also referred to as component 3)) (nonvolatile content: 35.4%) was obtained. The acid anhydride terminal group / aniline molar ratio of the component (A1-1) was 1.0, the number average molecular weight was 10,000, and the softening point was 70 ° C.

Production Example 5
A reaction vessel similar to that of Production Example 1 was charged with 490.00 g of BTDA-PF, 2597.00 g of cyclohexanone, and 519.40 g of methylcyclohexane, and heated to 60 ° C. Next, PRIAMINE1075 489.68 g and α, ω-bis (3-aminopropyl) polydimethylsiloxane (trade name “KF-8010”, manufactured by Shin-Etsu Chemical Co., Ltd.) 429.69 g were added, and the mixture was added at 130 ° C. for 12 hours. By performing an imidization reaction by applying it, a solution (nonvolatile content: 30.1%) of an acid anhydride group-terminated polyimide (A1-2) (hereinafter, also referred to as a component (A1-2)) was obtained. The acid component / amine component molar ratio of the component (A1-2) was 1.09, the number average molecular weight was 9500, and the softening point was 30 ° C.

Production Example 6
1400.00 g of the solution of the component (A1-2) was placed in the same reaction vessel as in Production Example 1, and the solvent was distilled off under reduced pressure until the nonvolatile content became 34.1%. Next, 3.81 g of Lipomin 8D was further charged, reacted at 140 ° C. for 12 hours, and then 346.55 g of cyclohexanone was added to the end-capped polyimide (1-4) (hereinafter, also referred to as (1-4) component. ) Solution (nonvolatile content 35.0%) was obtained. The acid anhydride terminal group / amine component molar ratio of the component (A1-2) was 1.0, the number average molecular weight was 11800, and the softening point was 30 ° C.

Production Example 7
4,4 ′-[Propane-2,2-diylbis (1,4-phenyleneoxy)] diphthalic acid dianhydride (trade name “BisDA1000”, manufactured by Evonik Japan Ltd.) was placed in the same reaction vessel as in Production Example 1. 310.00 g, cyclohexanone 992.00 g, and methylcyclohexane 124.00 g were charged and heated to 60 ° C. Then, 306.59 g of PRIAMINE1075 was added, and an imidization reaction was carried out at 130 ° C. for 15 hours to give a solution of the acid anhydride group-terminated polyimide (A1-3) (hereinafter, also referred to as “component (A1-3)”). (Nonvolatile content 35.7%) was obtained. The acid component / amine component molar ratio of the component (A1-3) was 1.05, the number average molecular weight was 15,000, and the softening point was 80 ° C.

Production Example 8
145.17 g of a solution of the component (A1-3) was placed in the same reaction vessel as in Production Example 1, and the solvent was distilled off under reduced pressure until the nonvolatile content became 36.6%. Next, 3.08 g of Lipomin 8D was further charged and reacted at 130 ° C. for 13 hours to give a solution of the end-capped polyimide (1-5) (hereinafter, also referred to as (1-5) component) (nonvolatile content: 38.7). %) Was obtained. The acid anhydride terminal group component / amine component molar ratio of the component (1-5) was 1.0, the number average molecular weight was 16000, and the softening point was 80 ° C.

Production Example 9
4,4 ′-[propane-2,2-diylbis (1,4-phenyleneoxy)] diphthalic acid dianhydride (trade name “BisDA1000”, manufactured by SABIC Japan Ltd.) was placed in the same reaction vessel as in Production Example 1. 1650.00 g and cyclohexanone 4298.22 g were charged and heated to 60 ° C. Then, PRIAMINE 1075 1068.95 g, 1,2-dimethoxyethane 1289.47 g, and methylcyclohexane 716.37 g were added, and the acid anhydride group-terminated polyimide (A1-4 ) (Hereinafter, also referred to as component (A1-4)) to obtain a solution (nonvolatile content: 32.0%). The acid component / amine component molar ratio of the component (A1-4) was 1.09, the number average molecular weight was 16000, and the softening point was 100 ° C.

Production Example 10
6506.92 g of a solution of the component (A1-4) was placed in the same reaction vessel as in Production Example 1, 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 charged and reacted at 130 ° C. for 14 hours to give a solution of the end-capped polyimide (1-6) (hereinafter, also referred to as component (1-6)) (nonvolatile content 35. 7%). The acid anhydride terminal group / amine component molar ratio of the component (A1-4) was 1.0, the number average molecular weight was 16500, and the softening point was 100 ° C.

<Preparation of polyimide adhesive>
Example 1
7. Solution of component (1-1) 100.00 g, N, N, N ′, N′-tetraglycidyl xylylenediamine (Mitsubishi Gas Chemical Co., Inc., trade name “TETRAD-X”, epoxy equivalent 95 g / eq) 8. 98 g and 20.00 g of toluene were mixed and stirred well to obtain an adhesive having a nonvolatile content of 34.8%.

Example 2
A solution of the component (1-2) (100.00 g), TETRAD-X (8.80 g) and toluene (20.00 g) were mixed and stirred well to obtain an adhesive having a nonvolatile content of 34.2%.

Reference example 1
A solution of the component (1-3) (100.00 g), TETRAD-X (8.85 g) and toluene (20.00 g) were mixed and stirred well to obtain an adhesive having a nonvolatile content of 34.3%.

Example 3
A solution of the component (1-4) (100.00 g), TETRAD-X (8.75 g) and toluene (20.000 g) were mixed and stirred well to obtain an adhesive having a nonvolatile content of 34.0%.

Example 4
A solution of the component (1-5) (100.00 g), TETRAD-X (9.68 g) and toluene (30.00 g) were mixed and stirred well to obtain an adhesive having a nonvolatile content of 34.6%.

Example 5
A solution of the component (1-6) (100.00 g), TETRAD-X (8.93 g) and toluene (20.00 g) were mixed and stirred well to obtain an adhesive having a nonvolatile content of 34.6%.

Comparative Example 1
A solution of the component (A1-1) (100.00 g), TETRAD-X (7.75 g) and toluene (10.00 g) were mixed and stirred well to obtain an adhesive having a nonvolatile content of 32.9%.

Comparative example 2
A solution of the component (A1-2) (100.00 g), TETRAD-X (7.53 g) and toluene (10.00 g) were mixed and stirred well to obtain an adhesive having a nonvolatile content of 32.0%.

Comparative Example 3
A solution of the component (A1-3) (100.00 g), TETRAD-X (8.93 g) and toluene (20.00 g) were mixed and well stirred to obtain an adhesive having a nonvolatile content of 34.6%.

Comparative Example 4
A solution of component (A1-4) (100.00 g), TETRAD-X (8.00 g) and toluene (10.00 g) were mixed and stirred well to obtain an adhesive having a nonvolatile content of 33.9%.

<Measurement of loss elastic modulus of adhesive layer>
The adhesive of Example 1 was replaced with Naflon PTFE tape TOMBO No. It was coated on 9001 (Nichias Co., Ltd.), dried at room temperature for 12 hours, and then dried at 150 ° C. for 5 minutes to prepare an adhesive sheet of about 20 μm.

Then, this adhesive sheet is folded to produce 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.) is used to determine the temperature dependence of the loss elastic modulus. Was measured. The rate of temperature rise was 10 ° C / minute. The results are shown in Table 2 and FIG. Moreover, the said measurement was implemented also about the adhesive agent of another Example , a comparative example, and a reference example . The results are shown in Table 2.

<Measurement of dielectric constant and dielectric loss tangent of adhesive layer>
The adhesive of Example 1 was replaced with Naflon PTFE tape TOMBO No. It was coated on 9001 (Nichias Co., Ltd.), dried at room temperature for 12 hours, and then cured at 200 ° C. for 1 hour to obtain an adhesive sheet having a film thickness of 50 μm.

Then, the dielectric sheet and the dielectric loss tangent at 10 GHz of the adhesive sheet were measured according to JIS C2565 using a commercially available dielectric constant measuring device (cavity resonator type, manufactured by ATI). Further, the adhesives of other Examples , Comparative Examples and Reference Examples were also measured in the same manner. The results are shown in Table 2.

<Measurement of heat-resistant adhesiveness of adhesive layer>
The adhesive of Example 1 was applied to a mirror surface of an electrolytic copper foil having a thickness of 18 μm (trade name “F2-WS”, manufactured by Furukawa Electric Co., Ltd., roll shape having a width of 25.4 cm) and a thickness after drying of 15 μm. After coating with a gap coater so as to be dried at 150 ° C. for 5 minutes, a resin-coated copper foil was obtained.

Next, F2-WS was superposed on the adhesive surface of the resin-coated copper foil from the mirror surface side, and hot pressed under the conditions of a pressure of 4.5 MPa, 160 ° C. and 1 hour to prepare a bonded sample. Then, after subjecting this sample to heat treatment at 200 ° C. for 60 hours in the atmosphere, the peeling strength (N / cm) was measured according to JIS C 6481 (Copper clad laminate test method for flexible printed wiring boards). did. Further, the adhesives of other Examples , Comparative Examples and Reference Examples were also measured in the same manner. The results are shown in Table 2.

Claims (19)

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

(Wherein, Y represents a single _{bond, -SO 2 -, - CO -} , - O -, - O-C 6 H 4 -C (CH 3) 2 -C 6 H 4 -O- , or ^{-COO-Y 1} -OCO- ^{(Y 1} is _- shows a _{(CH 2) l - - (} l = 1~20) or _{-H 2 C-HC (-O-} C (= O) -CH 3) -CH 2.) the Represents.) The polyimide adhesive according to claim 1 or 2, wherein the ratio of the moles of the component (a1) to the moles of the component (a2) is 1 <[(a1) / (a2)] <1.2. The polyimide adhesive according to any one of claims 1 to 3, wherein the monomer group (α) further contains a diaminopolysiloxane (a3). The ratio of the moles of the component (a1) to the total moles of the components (a2) and (a3) is 1 <[(a1) / [(a2) + (a3)]] <1.2. Item 4. A polyimide-based adhesive. The ratio of the moles of the component (a2) to the total moles of the components (a2) and (a3) is 0.3 <[(a2) / [(a2) + (a3)]] <1. Item 4. A polyimide adhesive according to item 4 or 5. (A2) the amount of the component, (A1) from 0.8 to 1.2 mol per terminal acid anhydride group 1 mole of component, either a polyimide-based adhesive according to claim 1-6. (2) component, epoxy compounds, benzoxazine compounds, containing at least one selected from the group consisting of bismaleimide compound and cyanate ester compound, or a polyimide-based adhesive according to claim 1-7. The polyimide-based adhesive according to claim 8 , wherein the epoxy compound contains tetraglycidyl xylylenediamine having the following structure.

(In the formula, Z represents a phenylene group or a cyclohexenyl group.) (1) 100 parts by weight of the component with respect to (in terms of solid content), (2) component is is and (3) component 150 to 900 parts by weight in 11 to 900 parts by weight, of any one of claims 1-9 Polyimide adhesive. Filmy adhesive comprising any one of the polyimide adhesive agent according to claim 1-10. Adhesive layer composed of filmy adhesive of any one of polyimide adhesive or claim 11 of claim 1-10. An adhesive sheet comprising the adhesive layer according to claim 12 and a support film as constituent elements. A resin-coated copper foil comprising the adhesive layer according to claim 12 and a copper foil as constituent elements. A copper-clad laminate comprising the resin-coated copper foil according to claim 14 and one copper foil as constituent elements. A copper clad laminate comprising the resin-coated copper foil according to claim 14 and one insulating sheet as constituent elements. A printed wiring board having a circuit pattern formed on the copper foil surface of the copper clad laminate according to claim 15 or 16 . One printed wiring board or one printed circuit board which is a core substrate,
An adhesive layer according to claim 12 ,
One printed wiring board or one printed circuit board which is another base material,
Including as a component,
Multilayer wiring board. A method for manufacturing a multilayer wiring board, which includes the following steps 1 and 2.
Step 1: Contacting the polyimide adhesive according to any one of claims 1 to 10 or the film adhesive according to claim 11 with at least one surface of one printed wiring board or one printed circuit board which is a core substrate. According to the process for producing a substrate with an adhesive layer, the process 2: a process for laminating one printed wiring board or one printed circuit board on the substrate with an adhesive layer and crimping under heating and pressure.

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