KR20210077613A - Adhesive composition, film-like adhesive material, adhesive layer, adhesive sheet, copper foil with resin, copper-clad laminate, printed circuit board, and multilayer wiring board and method for manufacturing the same - Google Patents

Abstract

Provided are an adhesive composition, a film-like adhesive, an adhesive layer, an adhesive sheet, a copper foil with a resin, a copper-clad laminate, a printed wiring board, and a multi-layered wiring board, and a method for manufacturing the same. An objective of the present invention is to provide: an adhesive composition, which contains a reactant (A) of a monomer group including an acid dianhydride (a1) having an aromatic ring structure and/or an alicyclic structure and diamine (a2) including dimer diamine, a crosslinking agent (B) and a diene-based polymer (C), and which contains a diene-based monomer having a 1,2-vinyl structure as a monomer constituting the diene-based polymer (C); a film-like adhesive; an adhesive layer; an adhesive sheet; a copper foil with a resin; a copper-clad laminate; a printed wiring board; and a multi-layered wiring board; and a method for manufacturing the same. According to the present invention, the adhesive composition has excellent heat resistance against soldering.

Description

Adhesive composition, film adhesive, adhesive layer, adhesive sheet, resin-attached copper foil, copper clad laminate, printed wiring board, and multilayer wiring board and manufacturing method thereof {ADHESIVE COMPOSITION, FILM-LIKE ADHESIVE MATERIAL, ADHESIVE LAYER, ADHESIVE SHEET, COPPER FOIL WITH RESIN, COPPER-CLAD LAMINATE, PRINTED CIRCUIT BOARD, AND MULTILAYER WIRING BOARD AND METHOD FOR MANUFACTURING THE SAME}

The present disclosure relates to an adhesive composition, a film adhesive, an adhesive layer, an adhesive sheet, a resin-adhered copper foil, a copper-clad laminate, a printed wiring board, and a multilayer wiring board and a method for manufacturing the same.

In mobile communication devices such as mobile phones and smartphones, their base station devices, network-related electronic devices such as servers and routers, and large computers, it is necessary to transmit and process large amounts of information at low loss and high speed. Electrical signals handled by printed wiring boards are also becoming higher-frequency. However, since high-frequency electrical signals are easily attenuated, it is necessary to further reduce the transmission loss in the printed wiring board. Therefore, the adhesive composition generally used for a printed wiring board is required to have a low dielectric constant and a low dielectric loss tangent (hereinafter also referred to as a low dielectric characteristic).

In addition, as the lead-free (Pb-free) response of the solder material used for mounting components advances, the printed wiring board is required to have heat resistance against soldering at a reflow temperature of about 260°C. Moreover, before a reflow process, in order to suppress foaming or blistering by moisture absorption, a printed wiring board is dried in advance at the temperature of 100-120 degreeC in many cases. However, in order to improve production efficiency, the number of cases in which the solder reflow process is performed without pre-drying is increasing. Therefore, adhesives used for printed wiring boards are required to exhibit not only adhesion but also heat resistance to soldering.

As an adhesive composition excellent in adhesiveness and heat resistance to soldering and also having low dielectric properties, for example, in Patent Document 1, a film having a predetermined glass transition temperature, tensile breaking strength and tensile modulus of elasticity (film) The polyimide-based adhesive of 狀) is described.

Japanese Patent Laid-Open No. 7-197007

However, the adhesive shown in Patent Document 1 had insufficient low dielectric properties in the GHz band, and thus was an invention with room for improvement.

In the present disclosure, an adhesive composition having low dielectric properties with good adhesiveness and heat resistance against soldering, a film adhesive, an adhesive layer, an adhesive sheet, a resin-adhered copper foil, a copper clad laminate, a printed wiring board, and a multilayer wiring board and a method for manufacturing the same can provide

MEANS TO SOLVE THE PROBLEM This inventor discovered that the said subject could be solved with a predetermined|prescribed adhesive composition, as a result of repeating earnest examination.

The present disclosure provides the following items.

(Item 1)

A reaction product (A) of a monomer group comprising an acid dianhydride (a1) having an aromatic ring structure and/or an alicyclic structure, and a diamine (a2) including dimerdiamine;

a crosslinking agent (B), and

diene-based polymer (C)

As an adhesive composition comprising:

As a monomer constituting the diene-based polymer (C), an adhesive composition comprising a diene-based monomer having a 1,2-vinyl structure.

(Item 2)

The adhesive composition according to item 1, further comprising a curing agent (D).

(Item 3)

The adhesive composition according to item 1 or 2, further comprising a flame retardant (E).

(Item 4)

The adhesive composition according to any one of Items 1 to 3, further comprising a thermal radical polymerization initiator (F).

(Item 5)

A film adhesive comprising a heat-cured product of the adhesive composition according to any one of items 1 to 4.

(Item 6)

An adhesive layer comprising the adhesive composition according to any one of items 1 to 4 or the film adhesive according to item 5.

(Item 7)

An adhesive sheet comprising the adhesive layer and the support film according to item 6.

(Item 8)

A resin-attached copper foil comprising the adhesive layer and copper foil as described in item 6.

(Item 9)

The adhesive sheet described in item 7 and/or the copper foil to which the resin described in item 8 is attached, and

A copper clad laminate comprising at least one selected from the group consisting of a copper foil, an insulating sheet, and a support film.

(Item 10)

A printed wiring board having a circuit pattern on a copper-clad surface of the copper-clad laminate according to item 9.

(Item 11)

printed wiring board or printed circuit board (1);

The adhesive layer described in item 6, and

Printed wiring board or printed circuit board (2)

Multilayer wiring boards that contain in this order.

(Item 12)

A method of manufacturing a multilayer wiring board comprising the following steps 1 and 2.

Step 1: By bringing the adhesive composition described in any one of items 1 to 4 or the film adhesive described in item 5 into contact with at least one side of a printed wiring board or printed circuit board 1, a substrate with an adhesive layer is produced process to do

Step 2: A step of laminating a printed wiring board or a printed circuit board 2 on the substrate to which the adhesive layer is attached, and pressing under heating and pressure

By using the adhesive composition of the present disclosure, an adhesive composition having low dielectric properties with good adhesion and heat resistance to soldering, a film adhesive, an adhesive layer, an adhesive sheet, a resin-adhered copper foil, a copper clad laminate, a printed wiring board, and a multilayer A wiring board and a manufacturing method thereof can be provided.

Throughout the present disclosure, numerical ranges such as respective physical property values and content may be appropriately set (eg, by selecting from the values of the upper and lower limits described in each item below). Specifically, with respect to the numerical value α, when A1, A2, A3, etc. are exemplified as the lower limit of the numerical value α, and B1, B2, B3, etc. are exemplified as the upper limit of the numerical value α, the range of the numerical value α is A1 or more, A2 or more, A3 or more, B1 or less, B2 or less, B3 or less, A1 to B1, A1 to B2, A1 to B3, A2 to B1, A2 to B2, A2 to B3, A3 to B1, A3 to B2, A3 to B3, etc. This is exemplified. In addition, in this indication, "-" is used in the meaning which includes the numerical value described before and after that as a lower limit and an upper limit.

<(A) component>

Acid dianhydride (a1) having an aromatic ring structure and/or alicyclic structure of the present disclosure (hereinafter also referred to as “component (a1)”), and dimerdiamine (a2) (hereinafter also referred to as “component (a2)”) The reactant (A) (hereinafter also referred to as "component (A)") of the monomer group containing

<(a1) component>

(a1) As a component, various well-known things can be used without a special restriction|limiting. (a1) A substance exemplified as a component and a well-known thing as a (a1) component can be used individually or in combination of 2 or more types.

Examples of the acid dianhydride having an aromatic ring structure include those represented by the following general formula.

(In the formula,

X is a single bond, —SO ₂ —, —CO—, —O—, —O—C ₆ H ₄ —C(CH ₃ ) ₂ —C ₆ H ₄ —O—, —COO—X ₁ It represents an -OCO- or X _2.

X ₁ represents —(CH ₂ ) _I —(I=1 or more and 20 or less) or —H ₂ C—HC(—O—C(=O)—CH ₃ )—CH ₂ —.

X ₂ is the following formula

represents)

As an acid dianhydride having an aromatic ring structure, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, 4,4'-[propane-2,2-diylbis(1,4-phenyl) Renoxy)]diphthalic dianhydride, 2,2-bis(3,3',4,4'-tetracarboxyphenyl)tetrafluoropropanedianhydride, 2,2-bis(3,4-dicarboxyphenyl) propane dianhydride, 2,2'-bis (3,4-dicarboxyphenoxyphenyl) sulfonic anhydride, 2,2', 3,3'-biphenyltetracarboxylic dianhydride, 2,2-bis (2, 3-dicarboxyphenyl) propane dianhydride, pyromellitic dianhydride, 1,2,3,4-benzenetetracarboxylic anhydride, 1,4,5,8-naphthalenetetracarboxylic anhydride, 2,3,6,7- Naphthalenetetracarboxylic acid anhydride, 9,9'-bis[4-(3,4-dicarboxyphenoxy)phenyl]fluorene dianhydride, 9,9'-bis(3,4-dicarboxyphenoxy)fluorene acid Anhydride, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid anhydride, etc. are illustrated.

As the acid dianhydride having an alicyclic structure, bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 1,2,3,4-cyclohexanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclo Butanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, tetrahydrofuran-2,3,4,5-tetracarboxylic dianhydride, 5-(2,5-dioxotetrahydrofuryl) )-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride and the like.

As the acid dianhydride having an aromatic ring structure and an alicyclic structure, a product name "BzDA" (manufactured by JXTG Nippon Oil & Energy Corporation) and the like are exemplified.

As for the upper limit of content (solid content conversion) of (a1) component in 100 mass % of monomer groups which comprise (A) component, 80, 70, 60, 50, 40, 30, 20, 10, 5, 3 mass % etc. It is illustrated, and 70, 60, 50, 40, 30, 20, 10, 5, 3, 1 mass % etc. are illustrated as for a minimum. In one embodiment, as for content (solid content conversion) of (a1) component in 100 mass % of monomer groups which comprise (A) component, about 1-80 mass % is preferable.

<(a2) component>

(a2) A component is diamine containing dimer diamine. Dimerdiamine is exemplified by substituting primary amino groups for all carboxyl groups of cyclic or acyclic dimer acids obtained as dimers of unsaturated fatty acids. (a2) As a component, various well-known things can be used without a special restriction|limiting. (a2) A substance exemplified as a component and a well-known thing as a (a2) component can be used individually or in combination of 2 or more types.

As dimerdiamine, what is represented by the following structure is illustrated. In each formula, preferably m+n=6 or more and 17 or less, preferably p+q=8 or more and 19 or less, the broken line portion means a carbon-carbon single bond or a carbon-carbon double bond.

The dimerdiamine may be a commercially available product. As this product, product names "Versamine 551", "Versamine 552 (hydrogenated product of Versamin 551)" (Cognis Japan Ltd.), product names "PRIAMINE1075", "PRIAMINE1074" ' (manufactured by Croda Japan KK) and the like.

<Other diamines>

You may include the following diamine in the monomer group of (A) component other than the said dimer diamine. As diamines other than the said dimer diamine, the diamine provided with the hydrocarbon group of a chain structure, the diamine provided with an alicyclic structure, the diamine provided with an aromatic ring structure, etc. are illustrated.

1,3-diaminopropane, 1,2-diaminopropane, 1,2-diamino-2-methylpropane, 2,2-dimethyl-1,3-propanediamine as diamine having a chain hydrocarbon group , 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane and the like are exemplified.

Examples of the diamine having an alicyclic structure include 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, bis( aminomethyl) norbornane and the like are exemplified.

As the diamine having an aromatic ring structure, 3-aminobenzylamine, 4-aminobenzylamine, 4-(aminomethyl)benzylamine, 2,5-dimethyl-1,4-phenylenediamine, 4,4'-dia Examples include mino-2,2'-dimethylbibenzyl, 3,3'-diaminodiphenylmethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, and 1,5-diaminonaphthalene. do.

In one embodiment, the upper limit of content (solid content conversion) of dimerdiamine in 100 mass % of (a2) component 100, 90, 80, 70, 60, 50, 40, 30, 20, 10, 5 mass % etc. are illustrated, and 90, 80, 70, 60, 50, 40, 30, 20, 10, 5, 1 mass % etc. are illustrated as for a lower limit. In one embodiment, as for content (solid content conversion) of dimerdiamine in 100 mass % of (a2) component, about 1-100 mass % etc. are illustrated.

In one embodiment, the upper limit of content (solid content conversion) of other diamine in 100 mass % of (a2) component is 99, 90, 80, 70, 60, 50, 40, 30, 20, 10, 5, 1, 0.1 mass % etc. are illustrated, and 90, 80, 70, 60, 50, 40, 30, 20, 10, 5, 1, 0.1, 0 mass % etc. are illustrated as for a lower limit. In one embodiment, as for content (solid content conversion) of other diamine in 100 mass % of (a2) component, about 0-99 mass % etc. are illustrated.

(A) The upper limit of content (solid content conversion) of (a2) component in 100 mass % of monomer groups which comprises component is 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35 , 30, 25, 20 mass %, etc. are illustrated, and 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15 mass % etc. are illustrated as for a lower limit. In one embodiment, as for content (solid content conversion) of (a2) component in 100 mass % of monomer groups which comprise (A) component, about 15-90 mass % is preferable.

(A) The upper limit of the weight average molecular weight of the component is exemplified by 60000, 50000, 40000, 30000, 20000, 10000, 7500, 5500, and the like, and the lower limit is exemplified by 50000, 40000, 30000, 20000, 10000, 7500, 5000, etc. do. In one embodiment, as for the weight average molecular weight of (A) component, from a viewpoint of a dielectric characteristic, solvent solubility, and a softness|flexibility, about 5000-60000 are preferable. In the present disclosure, the weight average molecular weight can be calculated as a polystyrene conversion value measured by gel permeation chromatography (GPC).

99, 95, 90, 80, 70, 60, 50, 40, 30 mass % etc. are illustrated, as for the upper limit of content (solid content conversion) of (A) component in 100 mass % of adhesive compositions of this indication, a lower limit Silver 95, 90, 80, 70, 60, 50, 40, 30, 20 mass % etc. are illustrated. In one embodiment, as for content (solid content conversion) of (A) component in 100 mass % of adhesive compositions of this indication, about 20-99 mass % is preferable.

The lower limit of the softening point (°C) of the component (A) is exemplified by 230, 210, 190, 170, 150, 130, 110, 100, 90, 80, 70, etc. , the upper limit is exemplified by 250, 230, 210, 190, 170, 150, 130, 110, 100, 90, 80, etc. from being excellent in workability. In one embodiment, as for the softening point (degreeC) of (A) component, about 70-250 are preferable. In the present disclosure, the softening point is the profile of the storage modulus (G') and the profile of the loss modulus (G'') measured using a commercially available measuring device (product name "ARES-2KSTD-FCO-STD", manufactured by Rheometric Scientific). It points out the temperature at the point of intersection, ie, the point where tan δ becomes 1.

The upper limit of the molar ratio of the acid dianhydride and the total diamine (acid dianhydride/diamine) is 1.5, 1.4, 1.3, 1.2, 1.1, 1.0, etc., and the lower limit is 1.4, 1.3, 1.2, 1.1, 1.0, 0.9. etc. are exemplified. In one embodiment, the molar ratio of the acid dianhydride to the total diamine (acid dianhydride/diamine) is preferably about 0.9 to 1.5 from the viewpoint of solvent solubility and solution stability.

(A) A component can be manufactured by various well-known methods. (A) The manufacturing method of component contains the acid dianhydride and dimer diamine provided with an aromatic ring structure and/or an alicyclic structure, The monomer group which further contains suitably other diamines and other acid anhydrides, Preferably 50 Polyaddition reaction is performed at a temperature of about °C or more and 120 °C or less, more preferably about 80 °C or more and 100 °C or less, preferably about 5 hours or less, more preferably about 3 hours or less. In the process of obtaining water, the obtained polyaddition product is preferably at a temperature of about 80° C. or more and 250° C. or less, more preferably about 100° C. or more and 200° C. or less, preferably for 0.5 hours or more and 50 hours or less, further Preferably, the imidation reaction for about 1 hour or more and 20 hours or less, ie, the method including the process of dehydrating ring closure reaction, etc. are illustrated.

In the imidation reaction, various known reaction catalysts, dehydrating agents, and organic solvents to be described later can be used. Various known reaction catalysts, dehydrating agents, and organic solvents to be described later may be used alone or in combination of two or more. 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. Examples of the dehydrating agent include aliphatic acid anhydrides such as acetic anhydride and aromatic acid anhydrides such as benzoic anhydride.

The imide closure rate of the polyimide is not particularly limited. Here, "imide closure rate" means content of the cyclic imide bond in a polyimide, For example, it can determine by various spectroscopic means, such as NMR and IR analysis. From a viewpoint that adhesiveness and the heat resistance with respect to soldering become favorable, about 70 % or more is preferable and, as for the imide ring closure rate of polyimide, about 85 % or more and 100 % or less are more preferable.

<Crosslinking agent (B)>

A crosslinking agent (B) (henceforth "(B) component") is a thing other than (C)component, If it functions as a crosslinking agent of an adhesive agent, various well-known things can be used without particular restriction|limiting. A crosslinking agent can be used individually or in combination of 2 or more types of the substance exemplified as a crosslinking agent, and what is known as a crosslinking agent. The crosslinking agent is preferably at least one selected from the group consisting of epoxides, benzoxazines, bismaleimides and cyanate esters.

As the epoxide, various known ones can be used without particular limitation. As epoxides, phenol novolac-type epoxide, cresol novolac-type epoxide, bisphenol A-type epoxide, bisphenol F-type epoxide, bisphenol S-type epoxide, hydrogenated bisphenol A-type epoxide, hydrogenated bisphenol F-type epoxy epoxide, stilbene-type epoxide, triazine skeleton-containing epoxide, fluorene skeleton-containing epoxide, linear aliphatic epoxide, alicyclic epoxide, glycidylamine-type epoxide, triphenolmethane-type epoxide, Alkyl-modified triphenolmethane-type epoxide, biphenyl-type epoxide, dicyclopentadiene skeleton-containing epoxide, naphthalene skeleton-containing epoxide, arylalkylene-type epoxide, tetraglycidylxylylenediamine, dimer acid of the epoxide Dimer acid-modified epoxide, dimer acid diglycidyl ester, etc. which are modified products are illustrated. A commercially available product may be sufficient as an epoxide. As such products, "jER828", "jER834", "jER807" manufactured by Mitsubishi Chemical Corporation, and "ST" manufactured by NIPPON STEEL Chemical & Material Co., Ltd. -3000", "CELLOXIDE 2021P" manufactured by Daicel Corporation, "YD-172-X75" manufactured by Nittetsu Chemical & Materials, Ltd., MITSUBISHI GAS CHEMICAL COMPANY, INC.) product "TETRAD-X" etc. are illustrated.

In particular, tetraglycidyldiamine of the following structure has good compatibility with the polyimide. In addition, when it is used, the low loss modulus of the adhesive layer becomes easy, and its heat-resistance adhesiveness and low dielectric properties are also improved.

(In the formula, Y represents a phenylene group or a cyclohexylene group)

As the benzoxazine, various known ones can be used without particular limitation. As benzoxazine, 6,6- (1-methylethylidene) bis (3,4-dihydro-3-phenyl-2H-1,3-benzoxazine), 6,6- (1-methyl thylidene)bis(3,4-dihydro-3-methyl-2H-1,3-benzoxazine) and the like are exemplified. Moreover, a phenyl group, a methyl group, a cyclohexyl group, etc. may couple|bond with the nitrogen of an oxazine ring. A commercially available product may be sufficient as benzoxazine. As such products, “benzoxazine Fa type” and “benzoxazine Pd type” manufactured by SHIKOKU CHEMICALS CORPORATION, and “RLV-100” manufactured by AIR WATER INC. etc. are exemplified.

As the bismaleimide, various known ones can be used without particular limitation. As bismaleimide, 4,4'-diphenylmethanebismaleimide, m-phenylenebismaleimide, bisphenol A diphenyletherbismaleimide, 3,3'-dimethyl-5,5'-diethyl-4 ,4'-diphenylmethanebismaleimide, 4-methyl-1,3-phenylenebismaleimide, 1,6'-bismaleimide-(2,2,4-trimethyl)hexane, 4,4'- Diphenyl ether bis maleimide, 4,4'-diphenyl sulfone bis maleimide, etc. are illustrated. The bismaleimide may be a commercially available product. As this product, "BAF-BMI" which is a product of JFE Chemical Corporation, etc. are illustrated. Since bismaleimide not only functions as a crosslinking agent of a polyimide, but also functions as a crosslinking agent of (C)component, bismaleimide is a preferable crosslinking agent. Moreover, by including a bismaleimide in (B) component, a crosslinking density rises and there exists a tendency for the adhesiveness and heat resistance of the adhesive composition of this indication to become more favorable.

As the cyanate ester, various known ones can be used without particular limitation. As cyanate ester, 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, etc. are illustrated. The cyanate ester may be a commercially available product. Examples of the product include "PRIMASET BTP-6020S" manufactured by Lonza Japan Ltd. and the like.

As for the upper limit of content (solid content conversion) of the crosslinking agent in 100 mass % of adhesive compositions of this indication, 10, 5, 2, 1, 0.8, 0.6, 0.1, 0.05 mass % etc. are illustrated, and a lower limit is 5, 2, 1, 0.8, 0.6, 0.1, 0.05, 0.01 mass %, etc. are illustrated. In one embodiment, as for content (solid content conversion) of the crosslinking agent in 100 mass % of adhesive compositions of this indication, about 0.01-10 mass % is preferable.

<Diene-based polymer (C)>

The diene-based polymer (C) (hereinafter also referred to as “component (C)”) is a polymer obtained by polymerizing a monomer containing a diene-based monomer, which is a monomer having two carbon-carbon double bonds that are polymerizable unsaturated bonds. . (C)component should just contain the diene type monomer provided with a 1,2-vinyl structure as a monomer which comprises (C)component. When using only the diene type monomer which does not have a 1,2-vinyl structure as a monomer which comprises (C)component instead of (C)component, since sclerosis|hardenability of an adhesive composition is bad, it is unpreferable.

(C) As a component, various well-known things can be used without a special restriction|limiting. (C) As a component, a styrene-butadiene copolymer, polyisoprene, polybutadiene, a butadiene-isoprene copolymer, an isobutylene-isoprene copolymer, a butadiene-acrylonitrile copolymer, a styrene-isoprene copolymer, etc. are illustrated. (C) A commercially available product may be sufficient as a component. As the product, liquid butadiene styrene random copolymer (product names "RICON100", "RICON181", "RICON184" (CRAY VALLEY product)), liquid polybutadiene (product names "RICON150", "RICON154", " RICON156" (manufactured by CRAY VALLEY)) and the like. (C) What is known as the substance illustrated as component and (C)component can be used individually or in combination of 2 or more types.

(C) A component can be manufactured by various well-known methods. (C) As a manufacturing method of a component,

(1) a method of polymerizing a diene-based monomer (α) having a 1,2-vinyl structure;

(2) A method of copolymerizing a diene-based monomer (α) having a 1,2-vinyl structure with a diene-based monomer having a 1,2-vinyl structure and a polymerizable monomer (β) is exemplified. Here, when manufacturing (C)component, you may use various polymerization initiators, a randomizer, etc. as needed. In addition, when producing the component (C) by anionic polymerization using a lithium-based polymerization initiator, it is also possible to modify the living end of the polymer chain with various modifiers. When an alkylene oxide such as ethylene oxide is used as the modifier, a diene-based polymer having a hydroxyl group at both ends or one end can be obtained.

As a diene-based monomer (α) having a 1,2-vinyl structure, 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 1,3-penta Diene, 1,4-pentadiene, 2,4-dimethylpenta-1,3-diene, 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, acrylonitrile, divinylbenzene , 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene, etc. are illustrated.

As a monomer (β) capable of polymerization with a diene-based monomer having a 1,2-vinyl structure, a monomer having two or more polymerizable unsaturated bonds and not having a 1,2-vinyl structure (β-1); The monomer (β-2) etc. provided with one polymerizable unsaturated bond are illustrated.

As a monomer (β-1) having two or more polymerizable unsaturated bonds and not having a 1,2-vinyl structure, 2,3-pentadiene, 2,4-hexadiene, 2,5-dimethyl-2, 4-hexadiene and the like are exemplified.

A monomer (β-2) having one polymerizable unsaturated bond, a monomer having a chain structure and one polymerizable unsaturated bond (β-2-1), a cyclic structure and a polymerizable unsaturated bond A single monomer (β-2-2) and the like are exemplified.

As a monomer (β-2-1) having a chain structure and one polymerizable unsaturated bond, ethylene, propylene, butene, 2-methylpropene, 3-methyl-1-butene, 1,3-butadiene mono epoxides and the like are exemplified.

a monomer having a cyclic structure and one polymerizable unsaturated bond (β-2-2), a monomer having an aromatic ring structure and one polymerizable unsaturated bond (β-2-2-1); The monomer (β-2-2-2) etc. which are provided with another cyclic structure and are provided with one polymerizable unsaturated bond are illustrated. (C) Since it is thought that there exists a tendency which is more excellent in adhesiveness, it is preferable to include the monomer ((beta)-2-2) which is equipped with a cyclic structure and has one polymerizable unsaturated bond in (C)component, and an aromatic ring It is more preferable to include a monomer (β-2-2-1) having a structure and having one polymerizable unsaturated bond.

As a monomer (β-2-2-1) having an aromatic ring structure and one polymerizable unsaturated bond, styrene, 3-methylstyrene, 4-methylstyrene, 4-tert-butylstyrene, 2-phenyl- 1-propene and the like are exemplified.

As a monomer (β-2-2) having another cyclic structure and one polymerizable unsaturated bond, 1,2-epoxy-4-vinylcyclohexane, 1-vinylimidazole, 2-methyl -1-vinylimidazole, vinylcyclopentane, vinylcyclohexane, 2-vinylpyridine and the like are exemplified.

(C) As for the upper limit of the number average molecular weight (Mn) of component, 20000, 17500, 15000, 12500, 10000, 9000, 8000, 7000, 6000, 5000, 4000, 3000, 2000 etc. are illustrated, a lower limit is 17500, 15000 , 12500, 10000, 9000, 8000, 7000, 6000, 5000, 4000, 3000, 2000, 1000 and the like are exemplified. In one embodiment, as for the number average molecular weight (Mn) of (C)component, about 1000-20000 are preferable. (C) There exists a tendency for adhesiveness to become more excellent by making the number average molecular weight (Mn) of component below the said upper limit. In this indication, a number average molecular weight can be calculated|required as a polystyrene conversion value measured by gel permeation chromatography (GPC).

When the monomer (β) capable of polymerization with the diene-based monomer having the 1,2-vinyl structure is styrene, the upper limit of the content (styrene mol%) of the component (C) is 60, 50, 40, 30, 20, 10 mol%, etc. are illustrated, and 50, 40, 30, 20, 10, 5 mol%, etc. are illustrated as for a lower limit. In one embodiment, the content of styrene (styrene mol%) is preferably about 5 to 60 mol%.

(C) The upper limit of the content (1,2 vinyl mol%) of the diene-based monomer having a 1,2-vinyl structure of the component is 100, 95, 90, 85, 80, 75, 70, 60, 50, 40 , 30, 20 mol%, etc. are exemplified, and the lower limit is exemplified by 95, 90, 85, 80, 75, 70, 60, 50, 40, 30, 20, 10, and the like. In one embodiment, as for 1,2 vinyl mol% of (C)component, about 10-100 mol% is preferable. As for the adhesive composition of this indication, adhesiveness and/or a low dielectric property become favorable, so that 1,2 vinyl mol% of (C)component is high.

30, 20, 10, 5, 2, 1 mass % etc. are illustrated as for the upper limit of content (solid content conversion) of (C)component in 100 mass % of adhesive compositions of this indication, and a minimum is 20, 10, 5, 2 , 1, 0.5 mass %, etc. are illustrated. In one embodiment, as for content (solid content conversion) of (C)component in 100 mass % of adhesive compositions of this indication, about 0.5-30 mass % is preferable.

<curing agent (D)>

In one embodiment, when (B) component contains an epoxide, you may use together various well-known hardening|curing agent (D) (henceforth "(D) component") to the adhesive composition of this indication. . In the present disclosure, the “curing agent” is a curing agent that reacts with an epoxide.

(D) As a component, various well-known things can be used without a special restriction|limiting. (D) As a component, a phenol type hardening|curing agent, an active ester type hardening|curing agent, an amine type hardening|curing agent, an acid anhydride type hardening|curing agent, an imidazole type hardening|curing agent, etc. are illustrated. (D) What is known as a substance illustrated as a component and (D)component can be used individually or in combination of 2 or more types.

As the phenol-based curing agent, various known curing agents may be used without particular limitation. Examples of the phenolic curing agent include phenol novolac resin, cresol novolak resin, bisphenol A-type novolac resin, triazine-modified phenol novolac resin, phenolic hydroxyl group-containing phosphazene, and the like. A commercially available product may be sufficient as a phenolic hardening|curing agent. As the product, phenolic hydroxyl group-containing phosphazene (manufactured by Otsuka Chemical Co., Ltd., product name "SPH-100", etc.), novolac-type phenol (DIC Corporation) product “TD-2091”, manufactured by Meiwa Plastic Industries, Ltd. (“H-4”), biphenyl novolac-type phenol (“MEH-7851” manufactured by Meiwa Chemical Industries, Ltd.), aralkyl-type phenol compounds ("MEH-7800" manufactured by Meiwa Chemical Co., Ltd.) and phenols having an aminotriazine skeleton ("LA1356" and "LA3018-50P" manufactured by DIC Corporation) etc. are illustrated.

As the active ester-based curing agent, various known curing agents may be used without particular limitation. As an active ester-based curing agent, an active ester compound containing a dicyclopentadiene-type diphenol structure, an active ester compound containing a naphthalene structure, and phenol novolac as described in Japanese Patent Application Laid-Open No. 2019-183071 It is conceivable to use an active ester curing agent that is an acetylated product and an active ester curing agent that is a benzoyl product of phenol novolac. A commercially available product may be sufficient as an active ester type hardening|curing agent. As said product, product names "EPICLON HPC-8000-65T", "EXB-8150-65T" (made by DIC Corporation), etc. are illustrated. You may manufacture an active ester type hardening|curing agent by various well-known methods. As described in Japanese Patent No. 5152445, the active ester curing agent may be obtained by reacting a polyfunctional phenol compound with aromatic carboxylic acids.

As the amine-based curing agent, various known curing agents may be used without particular limitation. Examples of the amine-based curing agent include dicyandiamide, aliphatic amine, and the like.

As the acid anhydride-based curing agent, various known curing agents may be used without particular limitation. As an acid anhydride-based curing agent, succinic anhydride, phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, 3-methyl-hexahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride, or 4 -Methyl-hexahydrophthalic anhydride and hexahydrophthalic anhydride mixture, tetrahydrophthalic anhydride, methyl-tetrahydrophthalic anhydride, nadic anhydride, methylnadic anhydride, norbornane-2,3-dicarboxylic anhydride, methylnor Bornane-2,3-dicarboxylic acid anhydride, methylcyclohexene dicarboxylic acid anhydride, 3-dodecenyl succinic anhydride, octenyl succinic anhydride, etc. are illustrated.

As the imidazole-based curing agent, various known curing agents may be used without particular limitation. Examples of the imidazole-based curing agent include 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, and epoxy-imidazole adduct. is exemplified

As for the upper limit of content (solid content conversion) of (D)component in 100 mass % of adhesive compositions of this indication, 10, 5, 3, 1, 0.1, 0.05, 0.01, 0.005, 0.001, 0.0005 mass % etc. are illustrated, and a lower limit Silver 5, 3, 1, 0.1, 0.05, 0.01, 0.005, 0.001, 0.0005, 0.0001, 0 mass % etc. are illustrated. In one embodiment, as for content (solid content conversion) of (D)component in 100 mass % of adhesive compositions of this indication, about 0-10 mass % is preferable.

When an epoxide as a crosslinking agent and a curing agent are used in combination, a reaction catalyst may be further used in combination. As the reaction catalyst, various known ones can be used without particular limitation. Examples of the reaction catalyst include tertiary amines, imidazoles, organic phosphines, tetraphenylboron, and the like. Substances exemplified as reaction catalysts and known reaction catalysts can be used alone or in combination of two or more types.

As the tertiary amine, various known ones can be used without particular limitation. Examples of the tertiary amine include 1,8-diaza-bicyclo[5.4.0]undecene-7, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris(dimethylaminomethyl)phenol, and the like. .

As the imidazoles, various well-known ones can be used without particular limitation. Examples of the imidazoles include 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, and 2-heptadecylimidazole.

As the organic phosphine, various known ones can be used without particular limitation. As the organic phosphine, tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, phenylphosphine and the like are exemplified.

As tetraphenylboron, various well-known ones can be used without particular limitation. Examples of tetraphenylboron include tetraphenylphosphonium chloride/tetraphenylborate, 2-ethyl-4-methylimidazole/tetraphenylborate, and N-methylmorpholine/tetraphenylborate.

As for the upper limit of content (solid content conversion) of reaction catalyst in 100 mass % of adhesive compositions of this indication, 5, 3, 1, 0.1, 0.05, 0.01 mass % etc. are illustrated, and a lower limit is 3, 1, 0.1, 0.05, 0.01 , 0.005, 0 mass %, etc. are illustrated. In one embodiment, as for content (solid content conversion) of the reaction catalyst in 100 mass % of adhesive compositions of this indication, about 0-5 mass % is preferable.

<Flame Retardant (E)>

In one embodiment, you may include a flame retardant (E) (henceforth "(E) component") in the adhesive composition of this indication. (E) A substance exemplified as a component and a well-known thing as (E) component can be used individually or in combination of 2 or more types. (E) As for a component, a phosphorus type flame retardant, an inorganic filler, etc. are illustrated.

Examples of the phosphorus-based flame retardant (phosphorus-containing flame retardant) include polyphosphoric acid, phosphoric acid ester, and phosphazene derivatives not containing a phenolic hydroxyl group. Among the phosphazene derivatives, a cyclic phosphazene derivative is preferable from the viewpoints of flame retardancy, heat resistance, and bleed-out resistance. Examples of commercially available cyclic phosphazene derivatives include SPB-100 manufactured by Otsuka Chemical Co., Ltd., Rabitle FP-300B manufactured by FUSHIMI Pharmaceutical Co., Ltd., and the like.

Examples of the inorganic filler include a silica filler, a phosphorus filler, a fluorine-based filler, and an inorganic ion exchanger filler. Commercial products of inorganic fillers, FB-3SDC manufactured by Denka Company Limited, KTL-500F manufactured by KITAMURA LIMITED, IXE manufactured by TOAGOSEI CO., LTD. ADMAFINE SC-2500-SPJ, a product of Admatechs Company Limited, and the like are exemplified. (E) When an inorganic filler is included as a component, since it is excellent in laser processability that the particle diameter is 1 micrometer or less, it is especially preferable.

As for the upper limit of content (solid content conversion) of (E) component in 100 mass % of adhesive compositions of this indication, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5 mass % etc. are illustrated, and a lower limit Silver 45, 40, 35, 30, 25, 20, 15, 10, 5, 0 mass % etc. are illustrated. In one embodiment, as for content (solid content conversion) of (E) component in 100 mass % of adhesive compositions of this indication, about 0-50 mass % is preferable.

<Thermal radical polymerization initiator (F)>

As the thermal radical polymerization initiator (F) (hereinafter, also referred to as "component (F)"), various well-known ones can be used without particular limitation. (F) As a component, an azo compound, a peroxide, etc. are illustrated. (F) A substance exemplified as a component and a well-known thing as (F) component can be used individually or in combination of 2 or more types.

As an azo compound usable as a thermal radical polymerization initiator, 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azo Bis(2-methylbutyronitrile), 4,4-azobis(4-cyanovaleric acid), 2,2'-azobis(2-methylpropionamidine)dihydrochloride, 2,2'-azo Bis[2-(2-imidazolin-2-yl)propane]dihydrochloride, 2,2'-azobis(2-methylpropionic acid)dimethyl, etc. are illustrated.

As peroxides usable as the thermal radical polymerization initiator, peroxyketals, hydroperoxides, dialkylperoxides, diacylperoxides, peroxydicarbonates, peroxyesters and the like are exemplified.

As the peroxyketal, 1,1-di(tert-hexylperoxy)cyclohexane, 1,1-di(tert-butylperoxy)cyclohexane, 2,2-di(tert-butylperoxy)butane, etc. is exemplified

As the hydroperoxide, tert-butyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, p-mentane hydroperoxide, 1,1,3,3-tetramethylbutylhydride Roperoxide and the like are exemplified.

As dialkyl peroxide, dicumyl peroxide, tert-butylcumylperoxide, di-tert-butylperoxide, di-tert-hexylperoxide, 2,5-dimethyl-2,5-di(tert-butylperoxy) ) hexane, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane-3 and the like.

As diacyl peroxide, diisobutyryl peroxide, di(3,5,5-trimethylhexanoyl) peroxide, dilauroyl peroxide, disuccinic acid peroxide, dibenzoyl peroxide, etc. are illustrated. The diacyl peroxide may be a commercially available product. Examples of the product include product names “NYPER BMT-K40” and “Nyper BMT-M” (all manufactured by NOF CORPORATION).

Examples of the peroxydicarbonate include diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, and bis(4-tert-butylcyclohexyl)peroxydicarbonate.

As peroxyester, tert-butylperoxypivalate, 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane, 1,1,3,3-tetramethylbutylperoxy-2 -Ethylhexanoate, tert-hexylperoxy-2-ethylhexanoate, tert-butylperoxy-2-ethylhexanoate, tert-butylperoxylaurate, tert-butylperoxy-3,5, 5-trimethylhexanoate, tert-hexylperoxyisopropyl monocarbonate, etc. are illustrated.

As for the upper limit of content (solid content conversion) of (F) component in 100 mass % of adhesive compositions of this indication, 5, 4, 3, 2, 1, 0.5, 0.1, 0.08, 0.06, 0.04 mass % etc. are illustrated, and a lower limit Silver 4, 3, 2, 1, 0.5, 0.1, 0.08, 0.06, 0.04, 0.01, 0.005, 0 mass %, etc. are illustrated. In one embodiment, as for content (solid content conversion) of (F)component in 100 mass % of adhesive compositions of this indication, about 0-5 mass % is preferable.

<Organic solvent (G)>

In one embodiment, you may mix|blend the organic solvent (G) (henceforth "(G) component") with the adhesive composition of this indication. (G) What is known as a substance illustrated as a component and (G)component can be used individually or in combination of 2 or more types. (G) As a component, a ketone solvent, an aromatic solvent, an alcohol solvent, a glycol solvent, a glycol ether solvent, an ester solvent, a haloalkane solvent, an amide solvent, another petroleum solvent etc. are illustrated.

Examples of the ketone solvent include methyl ethyl ketone, acetyl acetone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone.

Examples of the aromatic solvent include toluene, xylene, product names “T-SOL100” and “T-SOL150” (all manufactured by JXTG Energy Corporation).

Examples of the alcohol solvent include methanol, ethanol, n-propanol, isopropanol, butanol, benzyl alcohol and cresol.

Examples of the glycol solvent include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, polyethylene glycol, and polypropylene glycol.

As a glycol ether solvent, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol di Ethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol monoisopropyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol monoiso butyl ether, ethylene glycol mono-t-butyl ether, bis(2-methoxyether) ether, etc. are illustrated.

Examples of the ester solvent include ethyl acetate, butyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, and propylene glycol monomethyl ether acetate.

As a haloalkane solvent, chloroform etc. are illustrated.

Examples of the amide solvent include dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, and N-methylcaprolactam.

Examples of other petroleum solvents include dimethyl sulfoxide and methylcyclohexane.

As for the upper limit of content of (G) component in 100 mass % of adhesive compositions of this indication, 70, 60, 50, 40, 30, 20, 15, 10, 5 mass % etc. are illustrated, a minimum is 60, 50, 40 , 30, 20, 15, 10, 5, 1, 0 mass % etc. are illustrated. In one embodiment, as for content of (G)component in 100 mass % of adhesive compositions of this indication, about 0-70 mass % is preferable.

<additive>

In the adhesive composition of the present disclosure, an additive that does not correspond to any of the polyimide, crosslinking agent, diene-based polymer, curing agent, flame retardant, thermal radical polymerization initiator, and organic solvent may be included as an additive.

Additives include a ring-opening esterification reaction catalyst, a dehydrating agent, a plasticizer, a weathering agent, an antioxidant, a heat stabilizer, a lubricant, an antistatic agent, a brightener, a colorant, a conductive agent, a mold release agent, A surface treatment agent, a viscosity modifier, a filler, etc. are illustrated.

In one embodiment, as for content (solid content conversion) of an additive, less than 1 mass part, less than 0.1 mass part, less than 0.01 mass part, 0 mass part etc. are illustrated with respect to 100 mass parts of adhesive compositions.

In another embodiment, less than 1 mass part, less than 0.1 mass part, less than 0.01 mass part, 0 mass part etc. are illustrated as content of an additive with respect to 100 mass parts (solid content conversion) of the said polyimide.

The adhesive composition of the present disclosure can be obtained by dissolving the polyimide, a crosslinking agent and a diene-based polymer, and, if necessary, a curing agent, a flame retardant, a thermal radical polymerization initiator and an additive in an organic solvent.

<Film-like adhesive>

In the present disclosure, there is provided a film adhesive comprising a heat-cured product of the adhesive composition. Methods for producing a film adhesive include a step of applying the adhesive composition to a suitable release paper, a step of curing by heating to volatilize an organic solvent, a step of peeling from the release paper, etc. are exemplified do. As for the thickness of the said film adhesive, about 3 micrometers or more and 40 micrometers or less is preferable. As for the release paper, a conventionally well-known thing etc. are illustrated.

<Adhesive layer>

In the present disclosure, an adhesive layer comprising the adhesive composition or the film adhesive is provided. When manufacturing the said adhesive layer, you may use together the said adhesive composition and various well-known adhesive agents other than the said adhesive composition. Similarly, you may use together the said film adhesive and various well-known film adhesives other than the said film adhesive. In addition, when producing the adhesive layer, the adhesive layer can be obtained by heat curing the adhesive composition and, if necessary, various known adhesives or the film adhesive and, if necessary, various known film adhesives.

<Adhesive sheet>

In the present disclosure, there is provided an adhesive sheet including the adhesive layer and the support film.

As the support film, a plastic film or the like is exemplified.

As plastics, polyester, polyimide, polyimide-silica hybrid, polyethylene, polypropylene, polyethylene terephthalate, polyethylene naphthalate, polymethyl methacrylate resin, polystyrene resin, polycarbonate resin, acrylonitrile-butadiene-styrene resin , an aromatic polyester resin obtained from ethylene terephthalate, phenol, phthalic acid, hydroxynaphthoic acid, and parahydroxybenzoic acid (liquid crystal polymer; product name “Vecstar”, Kuraray Co., Ltd. ), cycloolefin polymer, syndiotactic polystyrene resin (SPS), fluororesin (polytetrafluoroethylene (PTFE), perfluoroalkoxyalkane (PFA), polyvinylidene fluoride (PVDF), etc.) is exemplified Since the adhesive layer of the present disclosure has very good adhesiveness, it is possible to adhere and/or adhere well to a support film with poor adhesion or poor adhesion. Various well-known ones may be sufficient as the said hard-adhesion or non-adhesive support film. Examples of the non-adhesive and/or non-adhesive support film include a liquid crystal polymer (LCP), a cycloolefin polymer (COP), a syndiotactic polystyrene resin (SPS), and a fluororesin (PTFE, PFA, PVDF, etc.).

In addition, when applying the adhesive composition to the support film, various known application means may be employed. About 1 micrometer or more and 100 micrometers or less are preferable, and, as for the thickness after drying of an application layer, about 3 micrometers or more and 50 micrometers or less are more preferable. The adhesive layer of the adhesive sheet may be protected with various protective films.

<Copper foil with resin attached>

In the present disclosure, there is provided a copper foil to which a resin is attached including the adhesive layer and the copper foil. Specifically, the said copper foil with resin apply|coated or bonded the said adhesive composition or the said film adhesive to copper foil. As said copper foil, a rolled copper foil, an electrolytic copper foil, etc. are illustrated. About 1 micrometer or more and 100 micrometers or less are preferable, and, as for the thickness of copper foil, about 2 micrometers or more and 38 micrometers or less are more preferable. In addition, the copper foil may have been subjected to various surface treatments (roughing, rust prevention, etc.). As the antirust treatment, a so-called mirror finish treatment such as a plating treatment using a plating solution containing Ni, Zn, Sn or the like and a chromate treatment is exemplified. Moreover, various well-known methods are illustrated as an application|coating means. Since the adhesive composition of this indication has very good adhesiveness, even if it is a material which is hard to adhere and/or hard to adhere, like copper foil to which the mirror surface treatment was given, it can adhere|attach and/or adhere favorably.

Uncured may be sufficient as the adhesive layer of the said copper foil with resin, and what made it partially hardened or fully hardened under heating may be sufficient as it. The partially cured adhesive layer is in a so-called B stage. Moreover, as for the thickness of a contact bonding layer, about 0.5 micrometer or more and 30 micrometers or less is preferable. Moreover, it is also possible to apply|coat or bond an adhesive layer to both surfaces of copper foil, and to set it as copper foil with resin adhered to both surfaces.

<Copper clad laminate>

In the present disclosure, there is provided a copper clad laminate including the adhesive sheet and/or the copper foil to which the resin is attached, and at least one selected from the group consisting of a copper foil, an insulating sheet and a support film. A copper clad laminate is also called CCL(Copper Clad Laminate). A copper-clad laminated board is a thing made by pressure-bonding the copper foil with the said resin on at least one side or both surfaces of various well-known copper foils or an insulating sheet specifically, under heating. When bonding to one surface, you may crimp a thing different from the copper foil to which the said resin adhered to the other surface. Moreover, the number in particular of the copper foil with resin in the said copper clad laminated board, copper foil, and an insulating sheet is not restrict|limited.

In one embodiment, the insulating sheet is preferably a prepreg or the above supporting film. A prepreg refers to a sheet-like material in which a reinforcing material such as glass cloth is impregnated with a resin and cured 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 used. As for the thickness of the said insulating sheet, about 20 micrometers or more and 500 micrometers or less are preferable. Heating/compression conditions are preferably about 150°C or more and 280°C or less (more preferably, about 170°C or more and 240°C or less), and preferably about 0.5 MPa or more and 20 MPa or less (more preferably, 1 MPa or more and 8 MPa or less). below).

<Printed wiring board>

In the present disclosure, there is provided a printed wiring board having a circuit pattern on the copper foil surface of the copper foil laminate. As a patterning means for forming a circuit pattern on the copper foil surface of a copper-clad laminate, a subtractive method, a semi-additive method, etc. are illustrated. As for the semi-additive method, the copper foil surface of a copper clad laminated board is patterned with a resist film, Then, electrolytic copper plating is carried out, the resist is removed, and the method of etching with alkaline solution is exemplified. In addition, the thickness of the circuit pattern layer in the said printed wiring board is not specifically limited. Moreover, a multilayer board can also be obtained by making the said printed wiring board as a core base material, and laminating|stacking the same printed wiring board or another well-known printed wiring board or printed circuit board on it. When laminating|stacking, the said adhesive composition and other well-known adhesive agents other than the said adhesive composition can be used together. In addition, the number of lamination|stacking in a multilayer board|substrate is not specifically limited. In addition, a via hole may be formed every time lamination|stacking, and the inside may be plated. The line/space ratio of the circuit pattern is preferably about 1 µm/1 µm to 100 µm/100 µm. Moreover, the height of the said circuit pattern is preferably about 1 micrometer or more and 50 micrometers or less.

<Printed circuit board>

In the present disclosure, there is provided a printed circuit board in which various well-known components such as capacitors are mounted on a printed wiring board.

<Multilayer wiring board>

In the present disclosure, there is provided a multilayer wiring board including a printed wiring board or printed circuit board 1, the adhesive layer, and a printed wiring board or printed circuit board 2 in this order. The printed wiring board of (1) and (2) may be the said printed wiring board, and various well-known things may be sufficient as it. Similarly, the printed circuit board of (1) and (2) may be the said printed circuit board, and various well-known things may be sufficient as it. The printed wiring boards of (1) and (2) may be the same or different. Similarly, the printed circuit boards of (1) and (2) may be the same or different.

<Method for manufacturing multilayer wiring board>

In the present disclosure, a method for manufacturing a multilayer wiring board including the following steps 1 and 2 is provided.

Step 1: A step of producing a base material with an adhesive layer by bringing the adhesive composition or the film adhesive into contact with at least one side of a printed wiring board or printed circuit board 1

Step 2: A step of laminating a printed wiring board or a printed circuit board 2 on the substrate to which the adhesive layer is attached, and pressing under heating and pressure

The said printed wiring board may be sufficient as the printed wiring board of said (1) and (2), and various well-known things may be sufficient as it. Similarly, the said printed circuit board may be sufficient as the printed circuit board of said (1) and (2), and various well-known things may be sufficient as it.

As the means for bringing the adhesive composition or the film adhesive into contact with at least one side of the printed wiring board or the printed circuit board 1, various well-known coating means, curtain coaters, roll coaters, laminators, presses, and the like are exemplified.

The heating temperature and pressing time after laminating the printed wiring board or the printed circuit board 2 on the substrate to which the adhesive layer is attached is determined by (a) contacting the adhesive composition or film-like adhesive of the present disclosure to at least one surface of the core substrate. After curing, heating at 70°C or higher and 200°C or lower, curing reaction over 1 minute or more and 10 minutes or less, and then (B) in order to advance the curing reaction of the crosslinking agent, 150°C or more and 250°C or less , it is preferable to further perform heat treatment for 10 minutes or more and 3 hours or less. Further, the pressure is preferably about 0.5 MPa or more and 20 MPa or less, more preferably about 1 MPa or more and 8 MPa or less in steps (A) and (B).

(Example)

Hereinafter, the present invention will be described in more detail with reference to Production Examples, Comparative Production Examples, Examples, Comparative Examples, Evaluation Examples and Comparative Evaluation Examples, but the present invention is not limited to these Examples. In addition, in the following description, unless otherwise specified, parts and % are based on mass.

In this example, the weight average molecular weight (Mw) was measured by gel permeation chromatography (GPC) under the following conditions.

(GPC measurement condition)

Model: Product name "HLC-8320GPC" (manufactured by Tosoh Corporation)

Column: Product name "TSKgel SuperHZM-M" (manufactured by Tosoh Corporation)

Developing solvent: THF

Flow rate: 0.35mL/min

Measuring temperature: 40℃

Detector: RI

Standard: Polystyrene

Sample preparation: 0.4% solution

<Production Example 1: Preparation of polyimide (A-1)>

In a reaction vessel equipped with a stirrer, a water fountain, a thermometer and a nitrogen gas inlet tube, 4,4'-[propane-2,2-diylbis(1,4-phenyleneoxy)]diphthalic acid Prepare 100.00 g of anhydride (product name "BisDA-1000" (hereinafter also referred to as "BisDA"), SABIC Innovative Plastics Japan Ltd. (SABIC JAPAN LLC)), 371.82 g of cyclohexanone, and heat the solution to 60°C. heated. Next, 100.82 g of C36 dimerdiamine (product name "PRIAMINE1075", manufactured by Croda Japan Co., Ltd.) was gradually added, then 74.36 g of methylcyclohexane was added, heated to 140° C., and imidized over 3 hours. By doing so, the solution (30.0% of non-volatile matter) of polyimide (A-1) was obtained. In addition, the molar ratio of the acid component/amine component of the polyimide resin was 1.03, the softening point was 80° C., and the weight average molecular weight was 40000.

<Production Example 2: Preparation of polyimide (A-2)>

In a reaction vessel equipped with a stirrer, a water fountain, a thermometer and a nitrogen gas inlet tube, 100.00 g of BisDA and 275.00 g of cyclohexanone were prepared, and the solution was heated to 60°C. Next, 67.25 g of C36 dimerdiamine (product name "PRIAMINE1075", manufactured by Croda Japan Co., Ltd.) and 1,3-bis(aminomethyl)cyclohexane (product name "1,3-BAC", Mitsubishi Gas Chemical Corporation) After gradually adding 8.34 g (manufactured by Geisha), 45.83 g of methylcyclohexane and 82.50 g of ethylene glycol dimethyl ether (DMG) are added, heated to 140° C. and imidized over 3 hours, whereby polyimide (A) -2) (non-volatile content 30.0%) was obtained. In addition, the molar ratio of the acid component/amine component of the polyimide resin was 1.05, the softening point was 100° C., and the weight average molecular weight was 30000.

<Production Examples 3-4: Preparation of polyimides (A-3) to (A-4)>

In Production Examples 3 to 4, polyimides (A-3) to (A-4) were obtained in the same manner as in Production Example 1 except that the composition was changed to the contents of Table 1.

The meaning of the terms in the said table|surface is as follows.

BisDA: 4,4'-[propane-2,2-diylbis(1,4-phenyleneoxy)]diphthalic dianhydride (SABIC Innovative Plastics Japan Co., Ltd. product)

BTDA: 3,3',4,4'-benzophenonetetracarboxylic dianhydride

PRIAMINE1075: C36 dimerdiamine (product of Croda Japan Co., Ltd.)

1,3-BAC: 1,3-bis(aminomethyl)cyclohexane (manufactured by Mitsubishi Gas Chemical Co., Ltd.)

DMG: Ethylene glycol dimethyl ether

<Example 1: Preparation of adhesive composition (1)>

100.0 g of a polyimide (A-1) solution, 0.93 g of a polyfunctional epoxy resin (product name “TETRAD-X”, manufactured by Mitsubishi Gas Chemical Co., Ltd.) as a crosslinking agent (B), liquid butadiene as a diene-based polymer (C)・Styrene random copolymer (product name “Ricon 100”, manufactured by CRAY VALLEY) 3.40 g, 2-ethyl-4-methylimidazole as curing agent (D) (product name “CUREZOL 2E4MZ-A”, Shikoku Kasei 0.0032 g (manufactured by Kogyo Corporation), 19.64 g of a methyl ethyl ketone dispersion (50% solid content) of a spherical silica filler (product name "FB-3SDC", manufactured by Denka Corporation) as a flame retardant (E) and phosphorus 12.27 g of methyl ethyl ketone dispersion (40% solids) of a flame retardant (product name "Exolit OP935", manufactured by Clariant Chemicals), and dicumyl peroxide (product name "PERCUMYL) as a thermal radical polymerization initiator (F)" D', 0.034 g of Nichiyu Corporation) was mixed, and the adhesive composition of 30.0% of a non-volatile matter was obtained by stirring well with 27.38 g of cyclohexanone which is an organic solvent (G).

<Examples 2-22 and Comparative Examples 1-3: Preparation of adhesive compositions (2) to (22) and (C1) to (C3)>

In Examples 2 to 22 and Comparative Examples 1 to 3, except that the composition of the adhesive composition was changed to the contents of Tables 2 to 4, it was carried out in the same manner as in Example 1, and the adhesive composition (2) having a non-volatile content of 30% ) to (22) and (C1) to (C3) were obtained.

<Evaluation Example 1-1: Preparation of copper clad laminate (1)>

The adhesive composition (1) is applied to a release film (product name "WH52-P25CM (white)", manufactured by Sun A. Kaken Co., Ltd.) with a gap coater so that the thickness after drying is 25 µm. After coating with a gap coater, it was dried at 150° C. for 5 minutes. The film adhesive was peeled from the release film, and one side of the obtained film adhesive was coated with a commercially available electrodeposited copper foil (product name "F2-WS", manufactured by Furukawa Electric Co., Ltd.) (film thickness 18 µm) ), and the other side was superimposed on a commercially available LCP film (product name "Bexstar", manufactured by Kuraray Co., Ltd.), to prepare a laminate of LCP film-film-like adhesive-electrolytic copper foil. Next, the laminate was placed on a support for press, and hot-pressed from the electrodeposited copper foil side under conditions of a pressure of 2.5 MPa, 180° C. and 90 minutes to prepare a 10 cm×10 cm copper clad laminate 1 .

<Evaluation Examples 1-2 to 1-10 and Comparative Evaluation Examples 1-1 to 1-2: Preparation of copper clad laminates (2) to (10) and (C1) to (C2)>

In Evaluation Examples 1-2 to 1-10 and Comparative Evaluation Examples 1-1 to 1-2, the adhesive composition (1) was changed to the adhesive compositions (2) to (10) or (C1) to (C2). Except that, it carried out in the same manner as in Evaluation Example 1-1 to obtain copper clad laminates (2) to (10) and (C1) to (C2).

<Evaluation Example 2-1: Preparation of multilayer wiring board (1)>

The adhesive composition (6) was applied to a release film (product name "WH52-P25CM (white)", manufactured by Sanei Chemical Co., Ltd.) with a gap coater so that the thickness after drying was 25 μm, and then dried at 150° C. for 5 minutes. did it The film adhesive is peeled from the release film, and one side of the obtained film adhesive is applied to a commercially available flexible copper clad laminate (product name "2NUSR2518LJ1", Kunshan Aplus Tec. Corporation), PI: 1mil, Cu: 1/2 oz) on the copper foil side, the other side of the film adhesive is overlaid on the polyimide side of the other flexible copper foil laminate (product name "2NUSR2518LJ1"), flexible copper clad laminate - film adhesive - flexible copper clad laminate of the laminate was prepared. Next, the multilayer wiring board 1 of 10 cm x 10 cm was produced by putting the said laminated body on the support body for press, and heat-pressing under the conditions of a pressure of 2.5 MPa, 180 degreeC, and 90 minutes. In addition, since there is no circuit pattern on the copper foil surface of the flexible copper clad laminate, strictly speaking, the definition of the multilayer wiring board of the present disclosure does not fit. That is, the multilayer wiring board 1 is produced as a virtual model of the multilayer wiring board.

<Evaluation Examples 2-2 to 2-13 and Comparative Evaluation Examples 2-1 to 2-2: Preparation of multilayer wiring boards (2) to (13) and (C1) to (C2)>

Evaluation Examples 2-2 to 2-13 and Comparative Evaluation Examples 2-1 to 2-2, except that the adhesive composition (6) was changed to the adhesive compositions (11) to (22) or (C2) to (C3) Then, in the same manner as in Evaluation Example 2-1, multilayer wiring boards (2) to (13) and (C1) to (C2) were obtained.

<Performance evaluation (1): dielectric constant and dielectric loss tangent test>

After drying the adhesive compositions (1) to (22) and (C1) to (C3) on a release film (product name "WH52-P25CM (white)", manufactured by San-ei Chemical Co., Ltd.), a gap so that the thickness after drying is 25 µm After application with a coater, it was dried at 150° C. for 5 minutes. The film-like adhesive was peeled from the release film, fixed on a Teflon film, and cured at 180° C. for 90 minutes. With respect to the obtained sample, based on the perturbation method cavity resonance method, the permittivity and dielectric loss tangent at 10 GHz are measured with a commercially available permittivity measuring device (product name “Perturbation Method Specimen-Hole Closed Type) Cavity Resonance Method Analogue” Conductivity/dielectric loss tangent measurement system", manufactured by KEYCOM Corporation) and a network analyzer (product name "E8361A", manufactured by Agilent Technologies, Inc.) were combined and measured. The measurement results are shown in Tables 2 to 4.

<Performance evaluation (2): Adhesion test>

For the various copper clad laminates described in Evaluation Example 1 and the various multilayer wiring boards described in Evaluation Example 2, the peel strength (N/ cm) was measured. The measurement results are shown in Tables 2 to 4.

<Performance evaluation (3): Heat resistance test for soldering>

For the various copper clad laminates described in Evaluation Example 1 and the various multilayer wiring boards described in Evaluation Example 2, what was left still for 24 hours immediately after curing and at a temperature of 25°C and humidity of 25% was 288°C. The copper foil side of the solder pot was floated for 30 seconds with the side down, and after taking it out from the solder pot, the appearance change was evaluated according to the following criteria. The measurement results are shown in Tables 2 to 4.

(circle): There was no change at all in the copper clad laminated board 4 cm x 4 cm.

x: Foaming was seen in the whole surface of 4 cm x 4 cm of copper clad laminated board.

The meaning of the terms in the said table|surface is as follows.

TETRAD-X: polyfunctional epoxy resin (manufactured by Mitsubishi Gas Chemical Co., Ltd.)

BMI-3000H: m-phenylenebismaleimide (product of Daiwakasei Industry Co., LTD.)

BMI-1000H: 4,4'-diphenylmethanebismaleimide (manufactured by Daiwakasei Kogyo Co., Ltd.)

BMI-2300: polyphenylmethane maleimide (manufactured by Daiwakasei Kogyo Co., Ltd.)

Ricon-100: liquid butadiene styrene random copolymer (number average molecular weight: 4500, 1,2 vinyl mol%: 70 mol%, styrene content: 25 mol%, CRAY VALLEY product)

Ricon-181: liquid butadiene styrene random copolymer (number average molecular weight: 3200, 1,2 vinyl mol%: 30 mol%, styrene content: 28 mol%, CRAY VALLEY product)

Ricon-184: liquid butadiene styrene random copolymer (number average molecular weight: 8600, 1,2 vinyl mol%: 30 mol%, styrene content: 28 mol%, CRAY VALLEY product)

Ricon-150: liquid polybutadiene (number average molecular weight: 3900, 1,2 vinyl mol%: 70 mol%, CRAY VALLEY product)

Ricon-154: liquid polybutadiene (number average molecular weight: 5200, 1,2 vinyl mol%: 90 mol%, CRAY VALLEY product)

2E4MZ-A: 2-ethyl-4-methylimidazole (product name: Curesol 2E4MZ-A, manufactured by Shikoku Kasei Kogyo Co., Ltd.)

HPC-8000-65T: active ester resin (product name "EPICLON HPC-8000-65T", manufactured by DIC Corporation, solid content 65%)

FB-3SDC: Filler of spherical silica with an average particle diameter of 3 µm (manufactured by Denka Corporation) (50% dispersion)

Exolit OP935: Phosphorus-based flame retardant (manufactured by Clariant Chemicals) (40% dispersion)

SC-2500-SPJ: Surface-modified spherical silica with an average particle diameter of 0.5 μm (manufactured by Admatex, Inc.)

Percumyl D: Dicumyl peroxide (product of Nichiyu Co., Ltd.)

Perhexa (PERHEXA) 25B: 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane (manufactured by Nichiyu Corporation)

PERMENTA H: p-mentane hydroperoxide (manufactured by Nichiyu Corporation)

Claims (12)

A reaction product (A) of a monomer group comprising an acid dianhydride (a1) having an aromatic ring structure and/or an alicyclic structure, and a diamine (a2) containing dimerdiamine;
a crosslinking agent (B), and
diene-based polymer (C)
As an adhesive composition comprising:
As a monomer constituting the diene-based polymer (C), an adhesive composition comprising a diene-based monomer having a 1,2-vinyl structure.
According to claim 1,
Adhesive composition further comprising a curing agent (D).
3. The method of claim 1 or 2,
Adhesive composition further comprising a flame retardant (E).
4. The method according to any one of claims 1 to 3,
Adhesive composition further comprising a thermal radical polymerization initiator (F).
Claims 1 to 4 comprising a heat-cured product of the adhesive composition of any one of claims
film adhesive.
Claims 1 to 4 comprising the adhesive composition of any one of claims or the film adhesive of claim 5
adhesive layer.
Comprising the adhesive layer and the support film of claim 6
adhesive sheet.
Comprising the adhesive layer and copper foil of claim 6
Copper foil with resin attached.
The adhesive sheet of claim 7 and/or the copper foil to which the resin of claim 8 is attached, and
Containing at least one selected from the group consisting of copper foil, insulating sheet and support film
Copper clad laminate.
A copper clad laminate having a circuit pattern on the copper clad surface of claim 9
printed wiring board.
printed wiring board or printed circuit board (1);
The adhesive layer of claim 6, and
Printed wiring board or printed circuit board (2)
included in this order
multi-layer wiring board.
A method of manufacturing a multilayer wiring board comprising the following steps 1 and 2.
Step 1: By bringing the adhesive composition of any one of claims 1 to 4 or the film adhesive of claim 5 into contact with at least one side of a printed wiring board or printed circuit board 1, a substrate with an adhesive layer ( process of manufacturing 基材)
Step 2: A step of laminating a printed wiring board or a printed circuit board 2 on the substrate to which the adhesive layer is attached and pressing under heating and pressure