JP2016210915A - Thermosetting insulation resin composition, and insulation film with support, prepreg, laminated sheet and multilayer printed circuit board using the thermosetting insulation resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermosetting insulation resin composition which is halogen-free, has high glass transition temperature, is excellent in solder heat resistance, fire retardancy and copper foil adhesiveness and has a small dielectric constant and a small dielectric loss tangent, and to provide an insulation film with a support, a prepreg, a laminated sheet and a multilayer printed circuit board each using the thermosetting insulation resin composition.SOLUTION: There is provided the thermosetting insulation resin composition containing: a curing agent (A) having an acidic substituent represented by the general formula (1) and an N-substituted maleimide group; a curing agent (B) having an acidic substituent containing a structural unit represented by the general formula (2-1) and a structural unit represented by the general formula (2-2); and an epoxy resin (C).SELECTED DRAWING: None

Description

  The present invention relates to a thermosetting insulating resin composition suitably used for electronic parts and the like, specifically halogen-free, high glass transition temperature, excellent in solder heat resistance, flame retardancy and copper foil adhesion, and The present invention relates to a thermosetting insulating resin composition having a small relative dielectric constant and dielectric loss tangent, and an insulating film with a support, a prepreg, a laminate and a multilayer printed wiring board using the same.

  In recent years, in order to process a large amount of data at high speed, the frequency of signals has been increased in computers, information equipment terminals, and the like. As the frequency used increases, the transmission loss of electrical signals increases. Therefore, printed wiring boards mounted on these devices need to support higher signal frequencies, and substrate materials have dielectric properties that are effective in reducing propagation delay time and transmission loss (low dielectric constant, Low dielectric loss tangent) is required.

In addition, there is an active movement to regulate materials including electronic parts that may generate harmful substances during combustion due to increased environmental awareness. Bromine compounds have been used in conventional multilayer printed wiring boards to make them flame retardant. However, it is expected that these bromine compounds will not be used in the near future because they may generate harmful substances during combustion. Has been.
Lead-free solder that does not contain lead is also being put into practical use as a solder generally used for connecting electronic components to a multilayer printed wiring board. This lead-free solder has a higher use temperature than conventional eutectic solder by about 20 to 30 ° C. Therefore, the substrate material is required to have higher heat resistance than ever before.

With the increase in the capacity of the information described above, the density and the number of layers of the substrate are increasing. Since such a substrate is used for social infrastructure such as servers and routers, high reliability is required.
Furthermore, in copper-clad laminates and interlayer insulation materials, due to the recent demand for higher density, high copper foil adhesion for fine wiring formation, workability when processing such as drilling or punching, etc. Is needed.

Until now, in order to obtain a thermosetting resin composition having a small relative dielectric constant and dielectric loss tangent, there are a method of using an epoxy resin having a small relative dielectric constant, a method of introducing a cyanate group, a method of introducing polyphenyl ether, etc. Has been used.
Specifically, a resin composition using an epoxy resin (see Patent Document 1), a resin composition using a bismaleimide (see Patent Document 2), a resin composition using a cyanate ester (see Patent Document 3), Resin composition using styrene-butadiene copolymer or polystyrene in combination with triallyl cyanurate, triallyl isocyanurate, etc. (see Patent Documents 4 to 5), and resin composition using polybutadiene in combination (Patent Documents 6 and 7) A resin composition obtained by prereacting a modified polybutadiene having a functional group such as a hydroxyl group, an epoxy group, a carboxy group, or a (meth) acryl group with a bismaleimide and / or a cyanate ester (see Patent Document 8), Triallyl cyanurate on polyphenylene ether imparted or grafted with a compound having a heavy bond group Resin composition using triallyl isocyanurate, polybutadiene, etc. (see Patent Document 9 and Patent Document 10), reaction product of polyphenylene ether and unsaturated carboxylic acid or unsaturated acid anhydride, and bismaleimide A composition (see Patent Document 11) and the like have been proposed.
However, although these techniques can achieve a decrease in relative dielectric constant, it has been difficult to achieve both high heat resistance, high glass transition temperature, and halogen-free.

In order to reduce the thermal expansion coefficient in the insulating resin layer, generally, a method of filling a large amount of an inorganic filler having a small thermal expansion coefficient and reducing the thermal expansion coefficient of the entire insulating layer has been used (see Patent Document 12). However, such a method tends to cause many problems such as a decrease in fluidity and a decrease in insulation reliability.
Furthermore, introduction of an imide skeleton that is thought to be useful for heat resistance and low thermal expansion has also been attempted. For example, a thermosetting composition for build-up using an aromatic diamine having an imide group and an epoxy resin has been proposed. (See Patent Document 13).

JP 58-69046 A JP-A-56-133355 Japanese Patent Publication No. 61-18937 JP-A-61-286130 JP-A-3-275760 JP-A-62-148512 JP 59-193929 A JP 58-164638 A JP-A-2-208355 JP-A-6-184213 JP-A-6-179734 JP 2004-182851 A JP 2000-17148 A

  Since the technique of Patent Document 13 uses a low molecular weight polyimide compound as a curing agent for an epoxy resin, most of them are not different from the characteristics of an epoxy resin in many cases, such as glass transition temperature, solder heat resistance, flame resistance, and copper foil adhesion. There has been a demand for a material that has a higher degree of compatibility between dielectric properties and dielectric properties.

  The present invention has been made in view of the above problems, is halogen-free, has a high glass transition temperature, is excellent in solder heat resistance, flame retardancy, and copper foil adhesion, and has a dielectric constant and dielectric loss tangent. It is an object to provide a thermosetting insulating resin composition having a small size, and an insulating film with a support, a prepreg, a laminate, and a multilayer printed wiring board using the same.

  As a result of diligent research to solve the above-mentioned problems, the present inventors, as a thermosetting insulating resin composition, have a curing agent having an acidic substituent having a specific structure and an N-substituted maleimide group, and an epoxy resin. It was found that the above problems can be solved by using and the present invention was completed.

That is, the present invention provides the following [1] to [8].
[1] (A) A curing agent having an acidic substituent and an N-substituted maleimide group represented by the following general formula (1); (B) a structural unit represented by the following general formula (2-1); The thermosetting insulating resin composition containing the hardening | curing agent which has an acidic substituent containing the structural unit represented by General formula (2-2), and (C) epoxy resin.

(In General Formula (1), each R ₁ independently represents an acidic substituent selected from a hydroxyl group, a carboxy group, and a sulfonic acid group, and each R ₂ independently represents a hydrogen atom or an aliphatic group having 1 to 5 carbon atoms. A hydrocarbon group or a halogen atom, x is an integer of 1 to 5, y is an integer of 0 to 4, and the sum of x and y is 5. R ₃ is independently a hydrogen atom or a carbon number of 1 Represents an aliphatic hydrocarbon group or a halogen atom of ˜5.)

(In General Formula (2-1), R ₄ represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and R ₅ each independently represents an aliphatic hydrocarbon group or aromatic carbon group having 1 to 5 carbon atoms. Represents a hydrogen group, and p represents an integer of 0 to _{3. In} the general formula (2-2), R ₁ , R ₂ , x and y are the same as those in the general formula (1).

[2] (B) A curing agent having an acidic substituent containing the structural unit represented by the general formula (2-1) and the structural unit represented by the general formula (2-2) is an aromatic vinyl. It is obtained by reacting a copolymer resin of a compound and maleic anhydride with an amine compound having an acidic substituent represented by the following general formula (3). The heat according to [1] above, which contains a structural unit derived from an aromatic vinyl compound represented by the formula (4-1) and a structural unit derived from maleic anhydride represented by the following general formula (4-2). Curable insulating resin composition.

(In general formula (3), R ₁ , R ₂ , x and y are the same as in general formula (1).)

(In general formula (4-1), R ₄ , R ₅ and p are the same as in general formula (2-1).)

[3] The thermosetting insulating resin composition according to [1] or [2], further including (D) a curing accelerator.
[4] The above [1] to [3], further comprising (E) 10 to 80 parts by mass of the inorganic filler with respect to 100 parts by mass of the total amount of the components (A) to (C) in terms of solid content. ] The thermosetting insulating resin composition in any one of.
[5] An insulating film with a support, in which a semi-cured film of the thermosetting insulating resin composition according to any one of [1] to [4] is formed on the surface of the support.
[6] A prepreg obtained by impregnating the thermosetting insulating resin composition according to any one of the above [1] to [4] into a fiber sheet-like reinforcing base material and then heating it.
[7] (1) Thermosetting insulating resin composition according to any one of [1] to [4], (2) Insulating film with support according to [5], (3) [6] ] The laminated board which has a thermosetting insulating resin layer formed using either of the prepregs of description.
[8] A multilayer printed wiring board produced using the laminated board according to [7].

  According to the present invention, a thermosetting insulating resin composition that is halogen-free, has a high glass transition temperature, is excellent in solder heat resistance, flame retardancy, and copper foil adhesion, and has a low relative dielectric constant and dielectric loss tangent, and An insulating film with a support, a prepreg, a laminate, and a multilayer printed wiring board using the same can be provided.

  Hereinafter, specific embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments, and may be implemented with appropriate modifications within the scope of the object of the present invention. can do.

[Thermosetting insulating resin composition]
The thermosetting insulating resin composition of the present invention comprises (A) a curing agent having an acidic substituent represented by the general formula (1) and an N-substituted maleimide group (hereinafter referred to as “(A) acidic substituent and N -A curing agent having a substituted maleimide group "or" component (A) ") and (B) the structural unit represented by the general formula (2-1) and the general formula (2-2). It is a thermosetting insulating resin composition containing a curing agent having an acidic substituent containing a structural unit (hereinafter also referred to as “component (B)”) and (C) an epoxy resin.

<(A) Curing agent having acidic substituent and N-substituted maleimide group>
The component (A) is a curing agent having an acidic substituent represented by the following general formula (1) and an N-substituted maleimide group.

In the general formula (1), each R ₁ independently represents an acidic substituent selected from a hydroxyl group, a carboxy group, and a sulfonic acid group, and each R ₂ independently represents a hydrogen atom, an aliphatic carbon atom having 1 to 5 carbon atoms. A hydrogen group or a halogen atom is shown, x is an integer of 1 to 5, y is an integer of 0 to 4, and the sum of x and y is 5. R ₃ each independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom.
Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R ₂ include an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 1 to 5 carbon atoms, and an alkynyl group having 1 to 5 carbon atoms. .

  Examples of such component (A) include (a-1) a maleimide compound having at least two N-substituted maleimide groups in one molecule (hereinafter referred to as “(a-1) maleimide compound” or “(a-1 ) Component ”) and (a-2) an amine compound having an acidic substituent represented by the following general formula (3) (hereinafter referred to as“ (a-2) amino compound ”or“ (a-2) component ”) And also obtained by reacting.

In general formula (3), R ₁ , R ₂ , x and y are the same as those in general formula (1).

(A-1) Examples of maleimide compounds include N, N′-ethylene bismaleimide, N, N′-hexamethylene bismaleimide, N, N ′-(1,3-phenylene) bismaleimide, N, N ′. -[1,3- (2-methylphenylene)] bismaleimide, N, N ′-[1,3- (4-methylphenylene)] bismaleimide, N, N ′-(1,4-phenylene) bismaleimide Bis (4-maleimidophenyl) methane, bis (3-methyl-4-maleimidophenyl) methane, 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethane bismaleimide, bis (4- Maleimidophenyl) ether, bis (4-maleimidophenyl) sulfone, bis (4-maleimidophenyl) sulfide, bis (4-maleimidophenyl) ketone, bis (4- Reimidocyclohexyl) methane, 1,4-bis (4-maleimidophenyl) cyclohexane, 1,4-bis (maleimidomethyl) cyclohexane, 1,4-bis (maleimidomethyl) benzene, 1,3-bis (4-maleimide) Phenoxy) benzene, 1,3-bis (3-maleimidophenoxy) benzene, bis [4- (3-maleimidophenoxy) phenyl] methane, bis [4- (4-maleimidophenoxy) phenyl] methane, 1,1-bis [4- (3-maleimidophenoxy) phenyl] ethane, 1,1-bis [4- (4-maleimidophenoxy) phenyl] ethane, 1,2-bis [4- (3-maleimidophenoxy) phenyl] ethane, 1 , 2-bis [4- (4-maleimidophenoxy) phenyl] ethane, 2,2-bis [4- ( -Maleimidophenoxy) phenyl] propane, 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane, 2,2-bis [4- (3-maleimidophenoxy) phenyl] butane, 2,2-bis [ 4- (4-maleimidophenoxy) phenyl] butane, 2,2-bis [4- (3-maleimidophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [4- (4-Maleimidophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 4,4-bis (3-maleimidophenoxy) biphenyl, 4,4-bis (4-maleimide) Phenoxy) biphenyl, bis [4- (3-maleimidophenoxy) phenyl] ketone, bis [4- (4-maleimidophenoxy) phenyl] ketone, 2,2′-bis (4-maleimidophenyl) disulfide, bis (4-maleimidophenyl) disulfide, bis [4- (3-maleimidophenoxy) phenyl] sulfide, bis [4- (4-maleimidophenoxy) phenyl] sulfide Bis [4- (3-maleimidophenoxy) phenyl] sulfoxide, bis [4- (4-maleimidophenoxy) phenyl] sulfoxide, bis [4- (3-maleimidophenoxy) phenyl] sulfone, bis [4- (4- Maleimidophenoxy) phenyl] sulfone, bis [4- (3-maleimidophenoxy) phenyl] ether, bis [4- (4-maleimidophenoxy) phenyl] ether, 1,4-bis [4- (4-maleimidophenoxy)- α, α-dimethylbenzyl] benzene, 1,3-bi [4- (4-Maleimidophenoxy) -α, α-dimethylbenzyl] benzene, 1,4-bis [4- (3-maleimidophenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4 -(3-maleimidophenoxy) -α, α-dimethylbenzyl] benzene, 1,4-bis [4- (4-maleimidophenoxy) -3,5-dimethyl-α, α-dimethylbenzyl] benzene, 1,3 -Bis [4- (4-maleimidophenoxy) -3,5-dimethyl-α, α-dimethylbenzyl] benzene, 1,4-bis [4- (3-maleimidophenoxy) -3,5-dimethyl-α, α-dimethylbenzyl] benzene, 1,3-bis [4- (3-maleimidophenoxy) -3,5-dimethyl-α, α-dimethylbenzyl] benzene, polyphenylmethanemaleimi Etc. The. These (a-1) components can be used individually or in combination of 2 or more types.
Among these, bis (4-maleimidophenyl) methane, bis (4-maleimidophenyl) sulfone, bis (4-maleimidophenyl) sulfide, and bis (4-maleimide) have a high reaction rate and can achieve higher heat resistance. Phenyl) disulfide, N, N ′-(1,3-phenylene) bismaleimide, 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane are preferred, and bis (4-maleimide) is inexpensive. Phenyl) methane and N, N ′-(1,3-phenylene) bismaleimide are more preferred, and bis (4-maleimidophenyl) methane is more preferred from the viewpoint of solubility in a solvent.

  (A-2) Examples of amino compounds include m-aminophenol, p-aminophenol, o-aminophenol, p-aminobenzoic acid, m-aminobenzoic acid, o-aminobenzoic acid, o-aminobenzenesulfone. Examples include acid, m-aminobenzenesulfonic acid, p-aminobenzenesulfonic acid, 3,5-dihydroxyaniline, 3,5-dicarboxyaniline and the like. Among these, m-aminophenol, p-aminophenol, and o-aminophenol are preferable from the viewpoint of low thermal expansion and solubility. These (a-2) amino compounds can be used alone or in combination of two or more.

The reaction between (a-1) maleimide compound and (a-2) amino compound is further performed by (a-3) a diamine compound having at least two primary amino groups in one molecule (hereinafter referred to as “(a-3) It may be carried out in the presence of “component”.
(A-3) Examples of the diamine compound having at least two primary amino groups in one molecule include p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, and 3-methyl-1,4-diaminobenzene. 2,5-dimethyl-1,4-diaminobenzene, 4,4′-diaminodiphenylmethane, 4,4′-diamino-3,3′-dimethyl-diphenylmethane, 4,4′-diamino-3,3′- Diethyl-diphenylmethane, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl sulfone, 3,3′-diaminodiphenyl sulfone, 4,4′-diaminodiphenyl ketone, benzidine, 3,3′-dimethyl-4, 4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybenzyl 2,2-bis (3-amino-4-hydroxyphenyl) propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanediamine, 2,2-bis (4-aminophenyl) propane 2,2-bis (4- (4-aminophenoxy) phenyl) propane, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 4,4′-bis (4-aminophenoxy) biphenyl, bis (4- (4-aminophenoxy) phenyl) sulfone, bis (4- (3-aminophenoxy) phenyl) sulfone, 9,9-bis (4-aminophenyl) fluorene and the like can be mentioned. These components (a-3) may be used alone or in admixture of two or more.

The reaction temperature of the (a-1) maleimide compound, the (a-2) amino compound, and the optionally used component (a-3) is preferably 70 to 200 ° C, more preferably 70 to 160 ° C. preferable. Moreover, it is preferable that reaction time is 0.1 to 10 hours, and it is more preferable that it is 1 to 6 hours.
(A-1) The amount ratio of the maleimide compound and (a-2) amino compound used is the sum of the (NH- ₂ ) group equivalents of the (a-2) amino compound and the optional (a-3) component, a-1) The relationship between the maleimide compound and the C = C group equivalent is preferably in the range of 0.1 ≦ [C = C group equivalent] / [-NH ₂ group equivalent] ≦ 10.0. More preferably, this relationship is 1.0 ≦ [C = C group equivalent] / [-NH ₂ group equivalent] ≦ 9.0, and 2.0 ≦ [C = C group equivalent] / [ More preferably, the total sum of —NH ₂ group equivalents ≦≦ 8.0.
When the amount ratio is 0.1 or more, gelation and heat resistance do not decrease, and when it is 10.0 or less, solubility in organic solvents, adhesion and heat resistance may decrease. Absent.

The organic solvent used in the reaction of (a-1) maleimide compound and (a-2) amino compound is not particularly limited, but alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, etc. Ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ester solvents such as ethyl acetate and γ-butyrolactone; ether solvents such as tetrahydrofuran; aromatic solvents such as toluene, xylene and mesitylene; dimethylformamide Nitrogen atom-containing solvents such as dimethylacetamide and N-methylpyrrolidone; sulfur atom-containing solvents such as dimethylsulfoxide, and the like. These may be used alone or in admixture of two or more.
Among these, from the viewpoint of solubility, cyclohexanone, propylene glycol monomethyl ether, methyl cellosolve, γ-butyrolactone, and dimethylacetamide are preferable, have low toxicity, and have high volatility and are difficult to remain as a residual solvent when producing a prepreg. Therefore, cyclohexanone, propylene glycol monomethyl ether, and dimethylacetamide are more preferable.

  The amount of the organic solvent used is preferably 25 to 1000 parts by mass per 100 parts by mass of the sum of (a-1) maleimide compound, (a-2) amino compound and optionally used (a-3) component. 40 to 700 parts by mass is more preferable. When the amount of the organic solvent used is 25 parts by mass or more, sufficient solubility can be obtained, and when it is 1000 parts by mass or less, synthesis does not take a long time.

In this reaction, a reaction catalyst can be optionally used. The reaction catalyst is not particularly limited, and examples thereof include amines such as triethylamine, pyridine, and tributylamine; imidazoles such as methylimidazole and phenylimidazole; and phosphorus-based catalysts such as triphenylphosphine. A mixture of seeds or more can be used.
The addition amount of the reaction catalyst is preferably 0.001 to 5% by mass with respect to the total mass of (a-1) maleimide compound and (a-2) amino compound.

  (A) The weight average molecular weight of the curing agent having an acidic substituent and an N-substituted maleimide group is preferably 400 to 8000, more preferably 400 to 5000, and still more preferably 400 to 3500 from the viewpoints of solubility and mechanical strength. It is. In addition, the weight average molecular weight in this invention is measured by the gel permeation chromatography (GPC) method (polystyrene conversion) using tetrahydrofuran as an eluent.

<(B) component>
The component (B) is a curing agent having an acidic substituent containing a structural unit represented by the following general formula (2-1) and a structural unit represented by the following general formula (2-2).

In the general formula (2-1), R ₄ represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and each R ₅ independently represents an aliphatic hydrocarbon group or aromatic hydrocarbon having 1 to 5 carbon atoms. A group, a methacryloyl group, an acryloyl group or a hydroxy group, and p represents an integer of 0 to 3. In general formula (2-2), R ₁ , R ₂ , x and y are the same as those in general formula (1).
Examples of the hydrocarbon group having 1 to 5 carbon atoms represented by R ₄ include an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 1 to 5 carbon atoms, and an alkynyl group having 1 to 5 carbon atoms.
Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R ₅ include an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 1 to 5 carbon atoms, and an alkynyl group having 1 to 5 carbon atoms. It is done.
Examples of the aromatic hydrocarbon group represented by R ₅ include a phenyl group and a naphthyl group.
In the component (B), the ratio of the number of moles m of the structural unit represented by the general formula (2-1) to the number of moles n of the structural unit represented by the general formula (2-2) (m: n ) Is preferably 12: 1 to 1: 1, more preferably 8: 1 to 2: 1, and even more preferably 6: 1 to 2: 1.

  In the component (B), the total content of the structural unit represented by the general formula (2-1) and the structural unit represented by the general formula (2-2) is preferably 50% by mass or more. Preferably it is 70 mass% or more, More preferably, it is 90 mass% or more, Most preferably, it is substantially 100 mass%.

  The component (B) comprises (b) a structural unit derived from an aromatic vinyl compound represented by the following general formula (4-1) and a structural unit derived from maleic anhydride represented by the following general formula (4-2). It can be obtained by reacting a copolymer resin to be contained (hereinafter also referred to as “(b) copolymer resin”) with an amine compound having an acidic substituent represented by the general formula (3).

In general formula (4-1), R ₄ , R ₅ and p are the same as in general formula (2-1).

(B) Ratio of the number of moles m ′ of the structural unit represented by the general formula (4-1) to the number of moles n ′ of the structural unit represented by the general formula (4-2) in the copolymer resin. (M ′: n ′) is the same as m: n.
(B) The total content of the structural unit represented by the general formula (4-1) and the structural unit represented by the general formula (4-2) in the copolymer resin is preferably 50% by mass or more. More preferably, it is 70% by mass or more, further preferably 90% by mass or more, and particularly preferably 100% by mass or less.

(B) The copolymer resin can be produced by copolymerizing an aromatic vinyl compound and maleic anhydride.
(B) Examples of the aromatic vinyl compound used as a raw material monomer for the copolymer resin include styrene, 1-methylstyrene, vinyltoluene, dimethylstyrene, and the like. These may be used alone or in combination of two or more. Can do.
Furthermore, in addition to the aromatic vinyl compound and maleic anhydride, various polymerizable components may be copolymerized. Examples of these components include vinyl compounds such as ethylene, propylene, butadiene, isobutylene, and acrylonitrile. A compound having a methacryloyl group or an acryloyl group such as a methacrylate such as methyl methacrylate and an acrylate such as methyl acrylate.
Moreover, you may introduce | transduce substituents, such as an allyl group, a methacryloyl group, an acryloyl group, and a hydroxy group, through the reaction using Friedel-Crafts reaction and metal catalysts, such as lithium, arbitrarily to a monomer.

<(C) Epoxy resin>
(C) As the epoxy resin, any resin having two or more epoxy groups in one molecule can be used without particular limitation. For example, bisphenol A, bisphenol F, biphenyl, novolak, Examples thereof include glycidyl ethers such as functional phenols, naphthalenes, alicyclics, and alcohols, glycidylamines, and glycidyl esters, and these can be used alone or in admixture of two or more.
Specifically, bisphenol F type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene ring-containing epoxy resin, anthracene type epoxy resin, biphenyl type epoxy resin in terms of dielectric properties, heat resistance, moisture resistance and copper foil adhesion , Biphenyl aralkyl type epoxy resin, phenol novolac type epoxy resin, and cresol novolac type epoxy resin are preferable, and they have a good low thermal expansion property and high glass transition temperature, so that naphthalene ring-containing epoxy resin, anthracene type epoxy resin, biphenyl type An epoxy resin, a biphenyl aralkyl type epoxy resin, and a phenol novolac type epoxy resin are more preferable.

The thermosetting insulating resin composition of the present invention is preferably as follows, with the total amount of components (A) to (C) in terms of solid content being 100 parts by mass.
The content of the component (A) is preferably 20 to 95 parts by mass and preferably 20 to 60 parts by mass with respect to 100 parts by mass of the total of the components (A) to (C) in terms of solid content. More preferred.
The content of the component (B) is preferably 20 to 95 parts by mass and preferably 20 to 60 parts by mass with respect to 100 parts by mass of the total of the components (A) to (C) in terms of solid content. More preferred.
The content of the component (C) is preferably 1 to 50 parts by mass and preferably 5 to 30 parts by mass with respect to 100 parts by mass of the total of the components (A) to (C) in terms of solid content. More preferred.

<(D) Curing accelerator>
The thermosetting insulating resin composition of the present invention may further contain (D) a curing accelerator.
Examples of the (D) curing accelerator include imidazoles and derivatives thereof, tertiary amines and quaternary ammonium salts, cycloamidine compounds, and phosphines.
Specifically, imidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 1-benzyl-2-methylimidazole, 2-heptadecylimidazole, 4,5 -Diphenylimidazole, 2-methylimidazoline, 2-phenylimidazoline, 2-undecylimidazoline, 2-heptadecylimidazoline, 2-isopropylimidazole, 2,4-dimethylimidazole, 2-phenyl-4-methylimidazole, 2-ethyl Imidazolines such as imidazoline, 2-isopropylimidazoline, 2,4-dimethylimidazoline, 2-phenyl-4-methylimidazoline; acrylonitrile, phenylenediisocyanate as masking agents for imidazole imino groups Imidazoles masked with silicate, toluidine isocyanate, naphthalene diisocyanate, methylene bisphenyl isocyanate, melamine acrylate, etc .; tertiary amines such as triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol; 1,5 A cycloamidine compound such as diazabicycloalkene such as diazabicyclo [4.3.0] nonene-5, 1,8-diazabicyclo [5.4.0] undecene-7, and derivatives thereof; triphenylphosphine, diphenyl ( p-tolyl) phosphine, tris (alkylphenyl) phosphine, tris (alkoxyphenyl) phosphine, tris (alkylalkoxyphenyl) phosphine, tris (dialkylphenyl) phosphine, tris (tri Rualkylphenyl) phosphine, tris (tetraalkylphenyl) phosphine, tris (dialkoxyphenyl) phosphine, tris (trialkoxyphenyl) phosphine, tris (tetraalkoxyphenyl) phosphine, trialkylphosphine, dialkylarylphosphine, alkyldiarylphosphine, etc. Examples thereof include organic phosphines or complexes of these organic phosphines and organic borons.
Among these, the isocyanate mask imidazole which masked imidazole with isocyanate is preferable from storage stability.
The content of the component (D) is preferably 0.1 to 5.0 parts by mass with respect to 100 parts by mass of the total of the components (A) to (C) in terms of solid content, and 0.2 to 1 More preferably, the content is 0.0 parts by mass.

<(E) Inorganic filler>
The thermosetting insulating resin composition of the present invention may further contain (E) an inorganic filler from the viewpoint of reducing the coefficient of thermal expansion of the thermosetting insulating resin layer.
(E) Examples of the inorganic filler include silica, mica, talc, short glass fiber, fine glass powder, hollow glass, antimony trioxide, calcium carbonate, quartz powder, aluminum hydroxide, and magnesium hydroxide. Among these, silica, aluminum hydroxide, and magnesium hydroxide are preferable from the viewpoint of dielectric properties, heat resistance, and flame retardancy, and silica and aluminum hydroxide are more preferable because of low thermal expansion. Moreover, since the high fluidity | liquidity is calculated | required by the insulating film for multilayer printed wiring boards in order to embed a wiring layer, (E) inorganic filler is preferable spherical shape.

  (E) The content of the inorganic filler is preferably 10 to 80 parts by mass and preferably 25 to 45 parts by mass per 100 parts by mass of the total amount of components (A) to (C) in terms of solid content. Is more preferable. By setting the content of the inorganic filler (E) to 80 parts by mass or less, the insulating resin layer becomes brittle and cracks do not occur in a temperature cycle test or the like.

  These (E) inorganic fillers may be treated with a coupling agent for the purpose of enhancing dispersibility, and are dispersed by a kneading method using a known kneading apparatus such as a kneader, a ball mill, a bead mill, or a three roll. be able to.

  (E) The average particle diameter of the inorganic filler is preferably 1 μm or less, more preferably 0.5 μm or less in consideration of the progress of miniaturization of wiring. (E) It can suppress that the surface unevenness | corrugation after the desmear process mentioned later does not become large too much that the average particle diameter of an inorganic filler is 1 micrometer or less, and an etching residue generate | occur | produces and insulation becomes inadequate. There is a tendency.

<(F) Phosphorus compound>
The thermosetting insulating resin composition of the present invention may further contain (F) a phosphorus compound from the viewpoint of ensuring flame retardancy.
(F) As a phosphorus compound, phosphate ester, phosphite ester, ammonium polyphosphate, nitrogen-containing phosphorus compound, trimethyl phosphate, triethyl phosphate, triphenyl phosphate, triphenyl phosphite, 1,3-bis- (2 ′ , 6′-dimethylphenyl) phosphoylbenzene, various organic phosphorus compounds such as 1,3-bis- (2 ′, 6′-diethylphenyl) phosphoylbenzene. Further, (C) a phosphorus-containing epoxy resin in which phosphorus is contained in an epoxy resin, (C) a phosphorus-containing phenol resin in which phosphorus is contained in a curing agent of the epoxy resin, or the like may be used.
(F) You may use a commercial item as a phosphorus compound. As a commercially available (F) phosphorus compound, “PX-200” (manufactured by Daihachi Chemical Industry Co., Ltd., trade name) and the like are commercially available.

<Other ingredients>
Furthermore, the thermosetting insulating resin composition of the present invention can optionally contain known thermoplastic resins, elastomers, flame retardants, organic fillers and the like as long as the effects of the present invention are not impaired.
Examples of the thermoplastic resin include polytetrafluoroethylene, polyethylene, polypropylene, polystyrene, polyphenylene ether resin, phenoxy resin, polycarbonate resin, polyester resin, polyamide resin, polyimide resin, xylene resin, petroleum resin, and silicone resin.
Examples of the elastomer include polybutadiene, polyacrylonitrile, epoxy-modified polybutadiene, maleic anhydride-modified polybutadiene, phenol-modified polybutadiene, carboxy-modified polyacrylonitrile, and the like.
Examples of the flame retardant include inorganic flame retardants such as antimony trioxide, aluminum hydroxide, and magnesium hydroxide.
Examples of the organic filler include organic powders such as silicone powder, polytetrafluoroethylene, polyethylene, polypropylene, polystyrene, and polyphenylene ether.

  Moreover, the thermosetting insulating resin composition of this invention can use an organic solvent arbitrarily as a dilution solvent. The organic solvent is not particularly limited. For example, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; alcohol solvents such as methyl cellosolve; ether solvents such as tetrahydrofuran; aromatics such as toluene, xylene, and mesitylene A group solvent etc. are mentioned, These can be used individually or in mixture of 2 or more types.

  Furthermore, the thermosetting insulating resin composition of the present invention is an ultraviolet absorber such as a benzotriazole type, an antioxidant such as a hindered phenol type, a styrenated phenol, a benzophenone, and the like, as long as the effects of the present invention are not impaired. Photopolymerization initiators such as benzyl ketals and thioxanthone, fluorescent brighteners such as stilbene derivatives, urea compounds such as urea silane, adhesion improvers such as silane coupling agents, and the like can be included.

The thermosetting insulating resin composition of the present invention can be suitably used for forming an insulating resin layer in the production of a multilayer printed wiring board. The thermosetting insulating resin composition of the present invention can form an insulating resin layer by being applied to a circuit board and cured in a varnish state, but industrially generally, an insulating film with a support, a prepreg, etc. It is preferably used in the form of a sheet-like laminated material.
Next, the insulating film with a support according to the present invention will be described.

[Insulating film with support]
The insulating film with support of the present invention is a film in which a semi-cured film of the thermosetting insulating resin composition of the present invention is formed on the surface of the support.
The insulating film with a support of the present invention comprises a thermosetting insulating resin composition containing components (A) to (C), or a thermosetting insulating resin composition containing components (D) to (F). After applying to the support film, drying and volatilizing the organic solvent, an insulating resin composition layer is formed by semi-curing (B-stage) the thermosetting insulating resin composition on the support film. It is a thing.
The semi-cured state of the insulating resin composition layer is within a range in which the adhesive force between the insulating resin composition layer and the circuit pattern substrate forming the insulating resin composition layer is ensured, and the embedding property (fluidity) of the circuit pattern substrate is ensured. A range is desirable.

As a coating method (coating machine), a die coater, a comma coater, a bar coater, a kiss coater, a roll coater, or the like can be used, and may be appropriately selected depending on the thickness of the insulating resin composition layer. As a drying method, heating, hot air blowing, or the like can be used.
The drying conditions are not particularly limited, but the drying is performed so that the content of the organic solvent in the insulating resin composition layer is 10% by mass or less, preferably 5% by mass or less.
The drying conditions vary depending on the amount of the organic solvent in the thermosetting insulating resin composition, the boiling point of the organic solvent, and the like. For example, the thermosetting insulating resin composition containing 30 to 60% by mass of the organic solvent is 50 to 150 ° C. Is dried for about 3 to 10 minutes to form a semi-cured film of the insulating resin composition layer. As drying conditions, suitable drying conditions may be set as appropriate by simple experiments in advance.

  The thickness of the insulating resin composition layer formed in the insulating film with a support is usually not less than the thickness of the conductor layer. The thickness of the conductor layer included in the circuit board is preferably 5 to 70 μm, more preferably 5 to 50 μm, and still more preferably 5 to 30 μm in order to reduce the thickness of the printed wiring board.

  Examples of the support in the insulating film with support include polyolefins such as polyethylene and polypropylene; polyesters such as polyvinyl chloride, polyethylene terephthalate (hereinafter also referred to as “PET”) and polyethylene naphthalate; films made of polycarbonate, polyimide, and the like. Can include release paper; metal foil such as copper foil and aluminum foil. In addition, you may give a mold release process to a support body and the protective film mentioned later other than a mat | matte process and a corona treatment.

Although the thickness of a support body is not specifically limited, It is preferable that it is 10-150 micrometers, and it is more preferable that it is 25-50 micrometers.
A protective film according to the support can be further laminated on the surface of the insulating resin composition layer on which the support is not in close contact. Although the thickness of a protective film is not specifically limited, For example, it is 1-40 micrometers. By laminating the protective film, foreign matter can be prevented from being mixed.
The insulating film with a support can be wound and stored in a roll shape.

[Prepreg]
The prepreg of the present invention is obtained by impregnating the fiber sheet-shaped reinforcing base material with the thermosetting insulating resin composition of the present invention and then heating it.
The prepreg of the present invention can be produced, for example, by impregnating the thermosetting insulating resin composition of the present invention into a fiber sheet-like reinforcing base material by a hot melt method or a solvent method and then heating to make a B stage. it can.

As the fiber sheet reinforcing substrate, for example, known materials used for various types of laminated sheets for electrical insulating materials can be used.
Examples of the material include inorganic fibers such as E glass, D glass, S glass, and Q glass; organic fibers such as polyimide, polyester, and polytetrafluoroethylene, and mixtures thereof.
These base materials have shapes, such as a woven fabric, a nonwoven fabric, a robink, a chopped strand mat, a surfacing mat, for example. These materials and shapes are selected depending on the intended use and performance of the molded article, and if necessary, two or more kinds of materials and shapes can be combined.
The thickness of the fiber sheet reinforcing substrate is not particularly limited. For example, a thickness of about 0.03 to 0.5 mm can be used, and the surface treated with a silane coupling agent or the like or mechanically opened. What performed the fiber process is suitable from the surface of heat resistance, moisture resistance, and workability.

In the above hot melt method, the thermosetting insulating resin composition is once coated on a coated paper having good releasability from the thermosetting insulating resin composition without dissolving the thermosetting insulating resin composition in an organic solvent. This is a method for producing a prepreg by laminating on a material or by directly coating a sheet-like reinforcing base material with a die coater without dissolving the thermosetting insulating resin composition in an organic solvent.
Also, the solvent method is to prepare a varnish by dissolving a thermosetting insulating resin composition in an organic solvent, and impregnating the thermosetting insulating resin composition by immersing a sheet-like reinforcing base material in the varnish, Then, it is the method of drying by heating etc.

[Laminated boards and multilayer printed wiring boards]
The laminated board of the present invention is a heat formed by using any one of (1) the thermosetting insulating resin composition of the present invention, (2) the insulating film with a support of the present invention, and (3) the prepreg of the present invention. It is a laminated board which has a curable insulating resin layer, and the multilayer printed wiring board of this invention is a multilayer printed wiring board manufactured using the laminated board of this invention.
Hereinafter, (2) an insulating film with a support of the present invention, or (3) a laminate having a thermosetting insulating resin layer formed using the prepreg of the present invention, and the laminate. A multilayer printed wiring board will be described.

<Method of using insulating film with support>
As a method of manufacturing a laminated board and a multilayer printed wiring board using the insulating film with a support of the present invention, for example, there is a method of laminating an insulating film with a support on one side or both sides of a circuit board using a vacuum laminator. Can be mentioned.
Examples of the substrate used for the circuit substrate include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate. In addition, a circuit board means here that the conductor layer (circuit) patterned was formed in the one or both surfaces of the above boards. Further, in a laminated board obtained by alternately laminating conductor layers and insulating layers, and a multilayer printed wiring board manufactured from the laminated board, a conductor layer in which one or both surfaces of the outermost layer of the multilayer printed wiring board are patterned ( Circuits) are also included in the circuit board here. The surface of the conductor layer may be subjected to a roughening process in advance by a blackening process or the like.

  In the above laminate, when the insulating film with a support has a protective film, after removing the protective film, the insulating film with a support and the circuit board are preheated as necessary, and the insulating film is pressurized and Crimp to circuit board while heating. In the insulating film with a support of the present invention, a method of laminating on a circuit board under reduced pressure by a vacuum laminating method is suitably used. Lamination conditions are not particularly limited. For example, the pressure bonding temperature (laminating temperature) is preferably 70 to 140 ° C., the pressure bonding pressure is preferably 0.1 to 1.1 MPa, and the air pressure is 20 mmHg (26.7 hPa) or less. It is preferable to laminate under reduced pressure. The laminating method may be a batch method or a continuous method using a roll.

  After laminating an insulating film with a support on a circuit board, after cooling to room temperature (25 ° C.), if the support is peeled off, the support is peeled off and thermally cured to form a thermosetting insulating resin layer on the circuit board. Can be formed. The conditions for thermosetting may be appropriately selected according to the type and content of the resin component in the thermosetting insulating resin composition, but for example, preferably at 150 to 220 ° C. for 20 to 180 minutes, more preferably It is selected in the range of 60 to 200 ° C. for 30 to 120 minutes.

  If the support is not peeled off after the thermosetting insulating resin layer is formed, it is peeled off here. Next, if necessary, holes are formed in the insulating layer formed on the circuit board to form via holes and through holes. Drilling can be performed, for example, by a known method such as drilling, laser, or plasma, or by combining these methods as necessary. However, drilling by a laser such as a carbon dioxide gas laser or a YAG laser is the most common method. is there.

Next, a conductor layer is formed on the thermosetting insulating resin layer by dry plating or wet plating. As the dry plating, a known method such as vapor deposition, sputtering, or ion plating can be used. In the case of wet plating, first, the surface of the cured thermosetting insulating resin layer is permanganate (potassium permanganate, sodium permanganate, etc.), dichromate, ozone, hydrogen peroxide / sulfuric acid, Roughening treatment is performed with an oxidizing agent such as nitric acid to form uneven anchors. Among these oxidizing agents, an aqueous sodium hydroxide solution (alkaline permanganate aqueous solution) such as potassium permanganate and sodium permanganate is preferably used.
Next, a conductor layer is formed by a method combining electroless plating and electrolytic plating. Alternatively, a plating resist having a pattern opposite to that of the conductor layer can be formed, and the conductor layer can be formed only by electroless plating. As a pattern formation method thereafter, for example, a known subtractive method, semi-additive method, or the like can be applied.

<Method using prepreg>
As a method for producing a laminated board and a multilayer printed wiring board using the prepreg of the present invention, for example, one or several prepregs of the present invention are stacked on a circuit board and sandwiched between metal plates through a release film. And press lamination under pressure and heating conditions.
Although it does not specifically limit as pressurization and heating conditions, Preferably, it is 20 to 100 minutes at the crimping pressure of 0.5-4 MPa and the temperature of 120-200 degreeC. Similarly to the insulating film with support, the prepreg can be laminated on a circuit board by a vacuum laminating method and then heat-cured.
Thereafter, the obtained laminated board can roughen the surface of the cured prepreg by the same method as described above, and then a conductor layer is formed by plating to produce a multilayer printed wiring board.

Next, the present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these descriptions.
In addition, the copper clad laminated board obtained by each Example and the comparative example measured and evaluated the performance with the following method.

(1) Glass transition temperature (Tg)
A 5 mm x 5 mm evaluation board from which the copper foil was removed by immersing the copper clad laminate in a copper etching solution was prepared, and thermal compression was performed by a compression method using a TMA test apparatus (manufactured by DuPont, trade name: TMA2940) Analyzed. After mounting the evaluation substrate on the apparatus in the Z direction, the measurement substrate was measured twice continuously under the measurement conditions of a load of 5 g and a heating rate of 10 ° C./min. The Tg indicated by the intersection of tangents with different thermal expansion curves in the second measurement was determined.
(2) Copper foil adhesion (copper foil peel strength)
By immersing the copper-clad laminate in a copper etching solution, an evaluation substrate was prepared by removing the copper foil leaving a 1 cm wide strip, and a tensile tester (manufactured by Shimadzu Corporation, trade name: AG-100) Was used to measure the peel strength (90 ° peel strength) of the band portion.
(3) Solder heat resistance A 5 cm × 5 cm evaluation board from which a copper foil was removed by immersing a copper clad laminate in a copper etching solution was prepared, and the pressure cooker test apparatus manufactured by Hirayama Manufacturing Co., Ltd. was used. After performing pressure-cooker treatment for 4 hours under the conditions of ℃ and 0.2 MPa (2 atm), after immersing the evaluation substrate in a solder bath at a temperature of 288 ° C. for 20 seconds, the solder heat resistance is observed by observing the appearance. evaluated.
(4) Flame Retardancy Evaluation A test piece cut out to 127 mm in length and 12.7 mm in width was prepared from an evaluation board from which a copper foil was removed by immersing a copper-clad laminate in a copper etching solution. Evaluation was made according to the method (Method V).
(5) Measurement of relative dielectric constant and dielectric loss tangent Measurement of relative dielectric constant and dielectric loss tangent of copper-clad laminate at 1 GHz by network analyzer (trade name: 8722C, manufactured by Hewlett-Packard Company) using the triplate structure linear line resonator method Carried out. The test piece size is 0.8mm thick x 200mm long x 50mm wide, and a straight line (line length 200mm) with a width of 1.0mm is formed by etching at the center of one side of one copper clad laminate. Copper was left on the entire surface to form a ground layer. In the other sheet, one surface was etched entirely, and the back surface was a ground layer. Next, a strip line was formed with the ground layers of the two copper-clad laminates on the outside. The measurement was performed at 25 ° C.

Production Example 1: Production of curing agent (A-1) Bis (4-maleimidophenyl) methane was added to a reaction vessel with a volume of 1 liter capable of heating and cooling, equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser. 174.0 g, 18.2 g of p-aminophenol and 330.0 g of dimethylacetamide were added and reacted at 150 ° C. for 2 hours to obtain a curing agent having an acidic substituent and an unsaturated N-substituted maleimide group (A-1) Solution was obtained.

Production Example 2: Production of curing agent (A-2) Bis (4-maleimidophenyl) methane was added to a reaction vessel having a volume of 2 liters that can be heated and cooled, equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser. 173.1 g, 4,4′-diaminodiphenylmethane 19.2 g, p-aminophenol 9.6 g, and dimethylacetamide 330.0 g were reacted at 150 ° C. for 2 hours to react with acidic substituents and unsaturated N -A solution of a curing agent (A-2) having a substituted maleimide group was obtained.

Production Example 3: Production of Curing Agent (B-1) A styrene-maleic anhydride copolymer resin was placed in a reaction vessel with a volume of 2 liters that can be heated and cooled, equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser. 196.0 g (product name: SMA EF-40, manufactured by CRAY VALLEY), 20.4 g of p-aminophenol, 500.0 g of toluene, reacted at 110 ° C. for 3 hours, and cured with an acidic substituent A solution of the agent (B-1) was obtained.

Production Example 4: Production of Curing Agent (B-2) A styrene-maleic anhydride copolymer resin was added to a reaction vessel with a volume of 2 liters that can be heated and cooled, equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser. (CRAY VALLEY, trade name: SMA EF-40) 372.4g, p-aminophenol 20.4g, toluene 500.0g was put and reacted at 110 ° C for 3 hours to cure with acidic substituents A solution of the agent (B-2) was obtained.

Production Example 5: Production of curing agent (A-3) Thermometer, stirrer, 174.0 g of bis (4-maleimidophenyl) methane and 12 p-aminophenol in a 1 liter reaction vessel capable of heating and cooling 0.2 g and 330.0 g of dimethylacetamide were added and stirred at room temperature for 2 hours to obtain a solution of a curing agent (A-3) containing bis (4-maleimidophenyl) methane and p-aminophenol.

Production Example 6: Production of Curing Agent (B-3) A styrene-maleic anhydride copolymer resin (with a thermometer, a stirrer, and a water quantifier with a reflux condenser provided in a reaction vessel with a volume of 1 liter that can be heated and cooled. 196.0 g of CRAY VALLEY, trade name: SMA EF-40), 20.4 g of p-aminophenol, and 500.0 g of toluene, and stirred at room temperature for 2 hours, styrene-maleic anhydride and p-amino A solution of a curing agent (B-3) containing phenol was obtained.

Examples 1-6, Comparative Examples 1-3
[Production of thermosetting insulating resin composition]
Using methyl ethyl ketone as a diluent solvent, the respective components were mixed at a blending ratio (parts by mass) shown in Table 1 to prepare a uniform thermosetting insulating resin composition varnish having a solid content of 65% by mass.

[Manufacture of insulating film with support]
Next, the thermosetting insulating resin composition varnish was uniformly coated on a PET film (thickness 38 μm) with a die coater so that the thickness of the insulating resin composition layer after drying was 40 μm, and at 110 ° C. Dried for 6 minutes. Subsequently, it wound up in roll shape, bonding the 15-micrometer-thick polypropylene film on the surface of the insulating resin composition layer. The obtained roll-shaped film was slit to a width of 507 mm to produce a sheet-like insulating film with a support having a size of 507 × 336 mm.

[Manufacture of prepreg and laminate]
A thermosetting insulating resin composition varnish is impregnated and coated on a 0.1 mm thick E glass cloth, and heated and dried at 160 ° C. for 10 minutes to give a prepreg having a thermosetting insulating resin composition content of 50% by mass. Obtained. Next, 4 sheets of this prepreg were stacked, 18 μm electrolytic copper foils were placed one above the other, and pressed at a pressure of 2.5 MPa and a temperature of 185 ° C. for 90 minutes to obtain a copper clad laminate.
About the copper clad laminated board produced in this way, performance was measured and evaluated by the above-mentioned method. The results are shown in Table 1.

The components (C) to (E) used in Table 1 are as shown below.
(C) Component N-673: Cresol novolak type epoxy resin (manufactured by DIC Corporation, epoxy equivalent 200 g / eq, softening point 78 ° C., trade name: N-673)
Component (D) G8009L: Isocyanate mask imidazole (Daiichi Kogyo Seiyaku Co., Ltd., trade name: G8009L)
(E) component F05-12: crushed silica (made by Fukushima Ceramic Co., Ltd.)

As is apparent from Table 1, the copper clad laminate obtained from the thermosetting insulating resin compositions of the examples according to the present invention is excellent in solder heat resistance, flame retardancy and dielectric properties, and in particular, the relative dielectric constant. Is 4.0 or less and the dielectric loss tangent is 0.009 or less, which indicates that the dielectric constant is low and the dielectric loss tangent is high and the reliability is high.
On the other hand, the copper-clad laminate obtained from the thermosetting insulating resin compositions of Comparative Examples 1 to 3 in which the component (A) and / or the component (B) was not used has solder heat resistance, flame retardancy, and dielectric properties. It turns out that it is inferior to any of these characteristics, and is inferior in reliability.

Claims (8)

(A) a curing agent having an acidic substituent represented by the following general formula (1) and an N-substituted maleimide group, (B) a structural unit represented by the following general formula (2-1), and the following general formula ( The thermosetting insulating resin composition containing the hardening | curing agent which has an acidic substituent containing the structural unit represented by 2-2), and (C) epoxy resin.

(In General Formula (1), each R ₁ independently represents an acidic substituent selected from a hydroxyl group, a carboxy group, and a sulfonic acid group, and each R ₂ independently represents a hydrogen atom or an aliphatic group having 1 to 5 carbon atoms. A hydrocarbon group or a halogen atom, x is an integer of 1 to 5, y is an integer of 0 to 4, and the sum of x and y is 5. R ₃ is independently a hydrogen atom or a carbon number of 1 Represents an aliphatic hydrocarbon group or a halogen atom of ˜5.)

(In general formula (2-1), R ₄ represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and R ₅ each independently represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms or an aromatic carbon group. A hydrogen group, a methacryloyl group, an acryloyl group or a hydroxy group, and p represents an integer of 0 to _{3. In} the general formula (2-2), R ₁ , R ₂ , x and y are the same as those in the general formula (1). Show things.) (B) A curing agent having an acidic substituent containing the structural unit represented by the general formula (2-1) and the structural unit represented by the general formula (2-2) is an aromatic vinyl compound and anhydrous It is obtained by reacting a copolymer resin with maleic acid and an amine compound having an acidic substituent represented by the following general formula (3), and the copolymer resin is represented by the following general formula (4) The thermosetting insulating resin according to claim 1, comprising a structural unit derived from an aromatic vinyl compound represented by -1) and a structural unit derived from maleic anhydride represented by the following general formula (4-2). Composition.

(In general formula (3), R ₁ , R ₂ , x and y are the same as in general formula (1).)

(In general formula (4-1), R ₄ , R ₅ and p are the same as in general formula (2-1).)   Furthermore, (D) The thermosetting insulating resin composition of Claim 1 or 2 containing a hardening accelerator.   Furthermore, (E) Inorganic filler is contained 10-80 mass parts with respect to 100 mass parts of total amounts of (A)-(C) component of solid content conversion, The any one of Claims 1-3. The thermosetting insulating resin composition described in 1.   The insulating film with a support body by which the film of the semi-hardened state of the thermosetting insulating resin composition of any one of Claims 1-4 is formed in the support body surface.   A prepreg obtained by heating a fiber sheet-like reinforcing base material after impregnating the thermosetting insulating resin composition according to any one of claims 1 to 4.   (1) The thermosetting insulating resin composition according to any one of claims 1 to 4, (2) the insulating film with a support according to claim 5, and (3) the prepreg according to claim 6. A laminate having a thermosetting insulating resin layer formed using any of them.   The multilayer printed wiring board manufactured using the laminated board of Claim 7.