WO2012117759A1 - Thermosetting composition, adhesive film, and multilayer printed circuit board - Google Patents

Abstract

A thermosetting composition that contains: an epoxy resin that has at least two epoxy groups per molecule; and a compound that has a triazole ring. Said compound also has: a group that has a radical-polymerizable double bond; and/or a group that can react with an epoxy group. The composition preferably also contains a phenol hardener.

Description

Thermosetting composition, adhesive film, and multilayer printed wiring board

The present invention relates to a thermosetting composition useful as an interlayer insulating material for a multilayer printed wiring board, an adhesive film using the thermosetting composition, and a multilayer printed wiring board using the thermosetting composition.

Current electronic devices are progressing in thickness, high-speed transmission, and high-density integration, and build-up multilayer printed wiring boards are often used as printed wiring boards used in these electronic devices.

A multilayer printed wiring board is usually manufactured by laminating an insulating material composed of a resin composition and a conductor circuit layer. As a connection method between conductor circuit layers, a via hole is formed by a laser method, a photo method, or the like, instead of the conventional drilling process. These methods achieve high-density integration by freely arranging small-diameter via holes.

Conventionally, most of the insulating material between layers used for a multilayer printed wiring board is a prepreg in which a glass cloth is impregnated with a thermosetting resin. However, with the recent demand for thinner multilayer printed wiring boards and higher density integration, insulating materials between layers that do not use a substrate such as glass cloth are required to make the insulating layers extremely thin.

Therefore, as a material applicable to an insulating material between layers used for a multilayer printed wiring board, from the group consisting of two types of epoxy resins, phenolic curing agents, phenoxy resins, polyvinyl acetal resins, polyamide resins and polyamideimide resins. An interlayer insulating resin composition for a multilayer printed wiring board containing at least one selected resin and an inorganic filler in a specific ratio, and a resin composition layer comprising the interlayer insulating resin composition on a support film An adhesive film for a multilayer printed wiring board formed in has been proposed (for example, see Patent Document 1). In addition, an epoxy resin composition containing an epoxy resin, a phenol resin having a specific hydroxyl group content, and a polyvinyl acetal resin, and a resin composition layer made of the epoxy resin composition are formed on a support film. An adhesive film has been proposed (see, for example, Patent Document 2).
However, these proposed techniques have a problem that insulation is not sufficient.

Also, in the manufacture of multilayer printed wiring boards, after via holes are formed by laser irradiation, metal plating is performed on the via holes. Before this metal plating processing is performed, on the lower conductor circuit formed by laser irradiation. In addition, a process for removing a resin residue (smear) remaining in the insulating layer, that is, a desmear process is performed. Desmear treatment is, for example, chemical treatment, that is, by immersing the multilayer substrate with via holes in a solution of a chemical oxidizing agent such as potassium permanganate or potassium dichromate, and dissolving and removing smears in the via holes. Done. If the desmear treatment is insufficient and the desmear property is not sufficiently secured, even if the metal plating is performed on the via hole, there is a risk that the conductivity between the upper layer conductor circuit and the lower layer conductor circuit may not be sufficiently secured due to smear. There is.
However, the proposed technique has a problem that the desmear property is not sufficient.

Furthermore, as described above, in the production of a multilayer printed wiring board, a metal plating process is performed. Therefore, the insulating layer is required to have good adhesion to the plating process, that is, anti-plating adhesion is required. However, the above proposed technique has a problem that the adhesion resistance to plating is not sufficient.

Therefore, at present, there is a demand for providing a thermosetting composition having excellent insulating properties, desmear properties, and plating-resistant adhesion.

JP 2005-154727 A JP 2007-254710 A

This invention makes it a subject to solve the said various problems in the past and to achieve the following objectives. That is, an object of the present invention is to provide a thermosetting composition having excellent insulating properties, desmearing properties, and plating-resistant adhesion.

Means for solving the problems are as follows. That is,
The thermosetting composition of the present invention comprises an epoxy resin having two or more epoxy groups in one molecule, at least one of a group having a radically polymerizable double bond and a group capable of reacting with an epoxy group, and a triazole ring. And a compound having:

According to the present invention, the above-described problems can be solved, the object can be achieved, and a thermosetting composition excellent in insulating properties, desmear properties, and plating-resistant adhesion properties can be provided.

(Thermosetting composition)
The thermosetting composition of the present invention comprises an epoxy resin having two or more epoxy groups in one molecule, at least one of a group having a radically polymerizable double bond and a group capable of reacting with an epoxy group, and a triazole ring. At least, preferably a phenolic curing agent, an inorganic filler, and, if necessary, other components.

<Epoxy resin having two or more epoxy groups in one molecule>
The epoxy resin having two or more epoxy groups in one molecule is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a cresol novolac epoxy resin, a phenol novolac epoxy resin, a tert- Butyl-catechol type epoxy resin, biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, naphthalene type epoxy resin, linear aliphatic epoxy resin, alicyclic epoxy resin, glycidylamine type epoxy resin, complex Examples thereof include cyclic epoxy resins, spiro ring-containing epoxy resins, and halogenated epoxy resins.
These may be used individually by 1 type and may use 2 or more types together.

The epoxy resin having two or more epoxy groups in one molecule includes two or more epoxy groups in one molecule and is liquid at 20 ° C., and three or more epoxy resins in one molecule. When used together with an aromatic epoxy resin having an epoxy group and solid at 20 ° C., sufficient flexibility is exhibited when the thermosetting composition is used in the form of an adhesive film. It is preferable in that an adhesive film (excellent in properties) can be formed, and at the same time, the breaking strength of the cured product of the thermosetting composition is improved and the durability of the multilayer printed wiring board is improved.

-Epoxy resin that has two or more epoxy groups in one molecule and is liquid at 20 ° C-
The epoxy resin having two or more epoxy groups in one molecule and being liquid at 20 ° C. is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a bisphenol A type epoxy resin, Examples thereof include bisphenol F type epoxy resin, phenol novolak type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, glycidylamine type epoxy resin, and alicyclic epoxy resin.
Among these, aromatic epoxy resins are preferable from the viewpoint of physical properties of the cured product.
In the present invention, the aromatic epoxy resin means an epoxy resin having an aromatic ring skeleton in the molecule.
Accordingly, the epoxy resin having two or more epoxy groups in one molecule and being liquid at 20 ° C. is an aromatic resin having two or more epoxy groups in one molecule and being liquid at 20 ° C. An epoxy resin is preferable.
These may be used individually by 1 type and may use 2 or more types together.

Note that the epoxy resin having two or more epoxy groups in one molecule and being liquid at 20 ° C. may be liquid at less than 20 ° C. When an epoxy resin having two or more epoxy groups in one molecule and being liquid at 20 ° C. is used instead of a solid epoxy resin at 20 ° C., normal temperature (20 ° C. to 30 ° C.) for handling an adhesive film Degree), it is difficult to obtain sufficient flexibility of the adhesive film, and the handleability of the adhesive film may be lowered. In addition, when laminating to a circuit board, sufficient fluidity of a thermosetting composition that only fills via holes and through holes may not be obtained.

Specific examples of the epoxy resin having two or more epoxy groups in one molecule and being liquid at 20 ° C. include HP4032 (manufactured by DIC), HP4032D (manufactured by DIC), and jER807 (Epicoat 807). (Mitsubishi Chemical Corporation), jER828EL (Epicoat 828EL) (Mitsubishi Chemical Corporation), jER152 (Epicoat 152) (Mitsubishi Chemical Corporation), YDF-170 (Nippon Chemical Co., Ltd.) and the like.

-Aromatic epoxy resin having 3 or more epoxy groups in one molecule and solid at 20 ° C-
The aromatic epoxy resin having three or more epoxy groups in one molecule and being solid at 20 ° C. is not particularly limited and may be appropriately selected depending on the intended purpose. For example, naphthalene type An epoxy resin, an epoxidized product of a condensate of phenols and an aromatic aldehyde having a phenolic hydroxyl group (trisphenol type epoxy resin), and the like can be mentioned.
These may be used individually by 1 type and may use 2 or more types together.
The aromatic epoxy resin having three or more epoxy groups in one molecule and solid at 20 ° C. may be solid at a temperature exceeding 20 ° C.

The epoxy equivalent of the aromatic epoxy resin having 3 or more epoxy groups in one molecule and solid at 20 ° C. is not particularly limited and can be appropriately selected according to the purpose. 230 g / eq or less is preferable, and 150 g / eq to 230 g / eq is more preferable. The epoxy equivalent (g / eq) is a molecular weight per one epoxy group.

As an aromatic epoxy resin having three or more epoxy groups in one molecule and solid at 20 ° C., specifically, HP4700 (EXA4700) (manufactured by DIC, naphthalene type tetrafunctional epoxy resin) , Epoxy equivalent 163 g / eq, solid at 20 ° C.), N-690 (manufactured by DIC, cresol novolac epoxy resin, epoxy equivalent 208 g / eq, solid at 20 ° C.), N-695 (manufactured by DIC, cresol Novolac type epoxy resin, epoxy equivalent 208 g / eq, solid at 20 ° C), EPPN-502H (manufactured by Nippon Kayaku Co., Ltd., trisphenol epoxy resin, epoxy equivalent 168 g / eq, solid at 20 ° C), NC7000L (Nipponization) Manufactured by Yakuhinsha Co., Ltd., naphthol novolac type epoxy resin, epoxy equivalent 228 g / eq, solid at 20 ° C.), NC 000H (manufactured by Nippon Kayaku Co., Ltd., biphenyl type epoxy resin, epoxy equivalent of 290 g / eq, solid at 20 ° C.), ESN185 (manufactured by Nippon Steel Chemical Co., Ltd., naphthol novolac type epoxy resin, epoxy equivalent of 275 g / eq, at 20 ° C. Solid), ESN475 (manufactured by Nippon Steel Chemical Co., Ltd., naphthol novolac type epoxy resin, epoxy equivalent 350 g / eq, solid at 20 ° C.), and the like.

As an epoxy resin having two or more epoxy groups in one molecule, an epoxy resin (first epoxy resin) having two or more epoxy groups in one molecule and being liquid at 20 ° C., and When the aromatic epoxy resin (second epoxy resin) having three or more epoxy groups in one molecule and solid at 20 ° C. is used in combination, the first epoxy resin (A1) and the above The mixing ratio (A1: A2) of the second epoxy resin (A2) is not particularly limited and may be appropriately selected depending on the intended purpose. However, the mass ratio is 1: 0.3 to 1: 2. Preferably, 1: 0.5 to 1: 1 is more preferable. When the ratio of the first epoxy resin (A1) in the mass ratio is too large, that is, when the first epoxy resin (A1) is more than A1: A2 = 1: 0.3, the thermosetting composition. When the adhesive film is used in the form of an adhesive film, the deaeration property during vacuum lamination is lowered and voids are likely to be generated. Further, the peelability of the protective film and the support film may be lowered during vacuum lamination, and the heat resistance after curing may be lowered. Moreover, it may be difficult to obtain sufficient breaking strength in the cured product of the thermosetting composition. On the other hand, when the ratio of the second epoxy resin (A2) in the mass ratio is too large, that is, when the second epoxy resin (A2) is more than A1: A2 = 1: 2, it is used in the form of an adhesive film. In such a case, sufficient flexibility may not be obtained, handling properties may deteriorate, and sufficient fluidity during lamination may be difficult to obtain.

The content of the epoxy resin having two or more epoxy groups in one molecule in the thermosetting composition is not particularly limited and may be appropriately selected depending on the intended purpose. The content is preferably 10% by mass to 50% by mass, more preferably 20% by mass to 40% by mass, and particularly preferably 20% by mass to 35% by mass with respect to the nonvolatile content of the composition. When the content is less than 10% by mass, the curability of the thermosetting composition may be lowered.

<Compound having at least one of a group having a double bond capable of radical polymerization and a group capable of reacting with an epoxy group and a triazole ring>
The compound having at least one of a group having a radical polymerizable double bond and a group capable of reacting with an epoxy group and a triazole ring includes a group having a radical polymerizable double bond and a group capable of reacting with an epoxy group. If it is a compound which has at least any of these and a triazole ring at least, there will be no restriction | limiting in particular, According to the objective, it can select suitably.

Examples of the radically polymerizable group having a double bond include an acryloyloxy group, a methacryloyloxy group, a vinylphenyl group, and an allyl group.

Examples of the group capable of reacting with the epoxy group include a carboxyl group, an amino group, and a mercapto group.

The triazole ring may be any of 1,2,3-triazole ring and 1,2,4-triazole ring.
1,2,3-triazole and 1,2,4-triazole are compounds represented by the following structural formula.

A compound having a triazole ring and at least one of a group having a radical polymerizable double bond and a group capable of reacting with an epoxy group, in other words, capable of reacting with a group having a radical polymerizable double bond and an epoxy group A compound in which an organic group having at least one of these groups is bonded to a triazole ring. The bonding position of the organic group to the triazole ring is not particularly limited and may be appropriately selected depending on the purpose, and may be bonded to a nitrogen atom of the triazole ring or bonded to a carbon atom. May be.

As the compound having at least one of a group having a radically polymerizable double bond and a group capable of reacting with an epoxy group and a triazole ring, a compound represented by the following general formula (I) is preferable.

However, in said general formula (I), X represents a triazole ring. Y represents an organic group having at least one of a group having a double bond capable of radical polymerization and a group capable of reacting with an epoxy group. n represents an integer of 1 to 3. When n is 2 to 3, Y may be the same or different.

In the general formula (I), Y may be bonded to a nitrogen atom of the triazole ring which is X, or may be bonded to a carbon atom.

In the general formula (I), n is preferably 1 to 2.

Y in the general formula (I) is preferably a group represented by the following general formula (II).

In the general formula (II), Y ₁ represents an m + 1 valent organic group having 2 to 25 carbon atoms. Z ₁ represents any of a carboxyl group, an acryloyloxy group, and a methacryloyloxy group. m represents an integer of 1 to 2. When m is 2, Z ₁ may be the same or different.

Z ₁ is preferably a carboxyl group in terms of insulation and plating-resistant adhesion. In addition, when m is 2, it is preferable that at least one of the Z ₁ is a carboxyl group.

The m + 1 valent organic group having 2 to 25 carbon atoms is not particularly limited and may be appropriately selected depending on the intended purpose. For example, at least one of a urea bond, an amide bond, an ester bond, and a thiourea bond is selected. And an m + 1 valent organic group having 2 to 25 carbon atoms. The carbon number of the organic group is preferably 2 to 20, and more preferably 2 to 15.

The molecular weight of the compound having a triazole ring and at least one of a group having a radically polymerizable double bond and a group capable of reacting with an epoxy group is not particularly limited and may be appropriately selected depending on the purpose. 90 to 1,000 is preferable, and 100 to 800 is more preferable.

Specific examples of the compound having at least one of a group having a radically polymerizable double bond and a group capable of reacting with an epoxy group and a triazole ring include a compound represented by the following formula.

The content in the thermosetting composition of the compound having a triazole ring and at least one of a group having a radically polymerizable double bond and a group capable of reacting with an epoxy group is not particularly limited and depends on the purpose. The amount is preferably 1.0% by mass to 20% by mass and more preferably 1.5% by mass to 10% by mass with respect to the nonvolatile content of the thermosetting composition. When the content is less than 1.0% by mass, sufficient insulating properties may not be exhibited. When the content exceeds 20% by mass, heat resistance may be deteriorated. When the content is within the more preferable range, it is advantageous in terms of both the cured film characteristics and the insulating properties.

<Phenolic curing agent>
The phenolic curing agent is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include phenol novolac resins, alkylphenol novolac resins, triazine structure-containing phenol novolac resins, bisphenol A novolac resins, and dicyclopentadiene types. Examples thereof include phenol resins such as phenol resins, Xylok type phenol resins, terpene-modified phenol resins, and polyvinyl phenols, naphthalene curing agents, and fluorene curing agents.
These may be used individually by 1 type and may use 2 or more types together.
A commercial item can be used as said phenol type hardening | curing agent. Examples of commercially available phenolic curing agents include Phenolite LA-7052 (manufactured by DIC, nonvolatile content 60% by mass).

The content of the phenolic curing agent is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 2% by mass to 60% by mass with respect to the nonvolatile content of the thermosetting composition. 5% by mass to 50% by mass is more preferable. When the content is less than 2% by mass, the properties of the cured film may be deteriorated and the heat resistance may be inferior, and when it exceeds 60% by mass, the toughness may be deteriorated. When the content is within the more preferable range, it is advantageous in that good cured film properties can be obtained.

In the phenolic curing agent, the ratio of the total number of epoxy groups present in the thermosetting composition and the total number of phenolic hydroxyl groups of the phenolic curing agent is 1: 0.5 to 1: 1. It is preferable to contain so that it may become .5. When the content rate of the said phenol type hardening | curing agent remove | deviates from this range, the heat resistance of the hardened | cured material of the said thermosetting composition may become inadequate.

<Inorganic filler>
The inorganic filler is not particularly limited and may be appropriately selected depending on the intended purpose. For example, silica, alumina, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, carbonic acid Examples thereof include magnesium, magnesium oxide, boron nitride, aluminum borate, barium titanate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, and calcium zirconate.
These may be used individually by 1 type and may use 2 or more types together.
Among these, silica is preferable.

The average particle size (d50) of the inorganic filler is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 5 μm or less, more preferably 0.04 μm to 2.0 μm. When the average particle diameter (d50) exceeds 5 μm, it may be difficult to perform stably when forming a circuit pattern finely on the conductor layer. The inorganic filler is preferably surface-treated with a surface treatment agent such as a silane coupling agent in order to improve moisture resistance.
The average particle size (d50) is defined as a particle size having an integrated value of 50% when expressed as an integrated (cumulative) weight percentage, and is defined as d50 (D50), for example. Using a dynamic light scattering photometer (trade name DLS7000, manufactured by Otsuka Electronics Co., Ltd.), the measurement principle can be a dynamic light scattering method, and the size distribution analysis method can be a cumulant method and / or a histogram method.

<Other ingredients>
The other component is not particularly limited as long as it does not impair the effects of the present invention, and can be appropriately selected according to the purpose. For example, phenoxy resin, polyvinyl acetal resin, polyamide resin, polyamideimide resin , Thermoplastic elastomers, curing accelerators, other resins, additives and the like.

-Phenoxy resin, polyvinyl acetal resin, polyamide resin, and polyamideimide resin-
The thermosetting composition preferably contains at least one selected from phenoxy resin, polyvinyl acetal resin, polyamide resin, and polyamideimide resin.
There is no restriction | limiting in particular as said phenoxy resin, According to the objective, it can select suitably. Specific examples of the phenoxy resin include, for example, FX280 (manufactured by Nippon Steel Chemical), FX293 (manufactured by Nippon Steel Chemical), YX8100 (manufactured by Mitsubishi Chemical), YL6954 (manufactured by Mitsubishi Chemical), YL6974 (Mitsubishi). Chemical Co., Ltd.).
There is no restriction | limiting in particular as said polyvinyl acetal resin, According to the objective, it can select suitably. Specific examples of the polyvinyl acetal resin include, for example, ESREC KS series (manufactured by Sekisui Chemical Co., Ltd.).
There is no restriction | limiting in particular as said polyamide resin, According to the objective, it can select suitably. Specific examples of the polyamide resin include KS5000 series (manufactured by Hitachi Chemical Co., Ltd.), BP series (manufactured by Nippon Kayaku Co., Ltd.), and the like.
There is no restriction | limiting in particular as said polyamideimide resin, According to the objective, it can select suitably. Specific examples of the polyamideimide resin include KS9000 series (manufactured by Hitachi Chemical Co., Ltd.).
These may be used individually by 1 type and may use 2 or more types together.
Among these, phenoxy resin and polyvinyl acetal resin are preferable.

The glass transition temperature of the phenoxy resin, polyvinyl acetal resin, polyamide resin, and polyamideimide resin is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 100 ° C or higher, preferably 100 ° C to 300 ° C. Is more preferable.

The glass transition temperature is determined according to the method described in JIS (Japanese Industrial Standards) K7197. In addition, the case where the glass transition temperature is not actually observed because the glass transition temperature is higher than the decomposition temperature is also included in the definition of “glass transition temperature of 100 ° C. or higher” in the present invention. The decomposition temperature is defined as a temperature at which the mass reduction rate when measured according to the method described in JIS K 7120 is 5%.

The phenoxy resin, polyvinyl acetal resin, polyamide resin, and polyamideimide resin have an important influence on the thermal fluidity during lamination of the thermosetting composition and the roughening property of the cured product by an oxidizing agent. In addition, when the glass transition temperature of the phenoxy resin, polyvinyl acetal resin, polyamide resin, and polyamideimide resin is less than 100 ° C., the mechanical strength of the cured product is insufficient, and inorganic filler is deposited on the surface of the cured product after roughening. It is difficult to obtain sufficient plating peel strength.

There is no restriction | limiting in particular as content of the said phenoxy resin, polyvinyl acetal resin, a polyamide resin, and a polyamideimide resin, Although it can select suitably according to the objective, With respect to the non volatile matter of the said thermosetting composition 2% by mass to 20% by mass is preferable. When the content is less than 2% by mass, the heat fluidity at the time of laminating the thermosetting composition becomes too large, the thickness of the insulating layer becomes uneven, and the cured product is sufficiently roughened. Sexuality may not be obtained. On the other hand, if the content exceeds 20% by mass, the thermal fluidity is too low and the thermosetting composition may not be sufficiently filled in via holes and through holes present in the circuit board.

-Thermoplastic elastomer-
There is no restriction | limiting in particular as said thermoplastic elastomer, According to the objective, it can select suitably, For example, styrene-type elastomer, olefin-type elastomer, urethane-type elastomer, polyester-type elastomer, polyamide-type elastomer, acrylic-type elastomer, silicone Based elastomers and the like. These may be used individually by 1 type and may use 2 or more types together.
These thermoplastic elastomers are composed of a hard segment component and a soft segment component. In general, the former contributes to heat resistance and strength, and the latter contributes to flexibility and toughness.
Examples of the styrene-based elastomer, olefin-based elastomer, urethane-based elastomer, polyester-based elastomer, polyamide-based elastomer, acrylic-based elastomer, silicone-based elastomer, and rubber-modified epoxy resin include, for example, paragraphs of JP-A-2009-014745. [0087] to [0095].
By adding the thermoplastic elastomer to the thermosetting composition, heat resistance, flexibility and toughness can be imparted to the thermosetting composition.

There is no restriction | limiting in particular as content in the said thermosetting composition of the said thermoplastic elastomer, Although it can select suitably according to the objective, 1 mass% with respect to the non volatile matter of the said thermosetting composition Is preferably 50% by mass, more preferably 2% by mass to 20% by mass, and particularly preferably 3% by mass to 10% by mass. When the content is less than 1% by mass, the toughness of the cured film may be inferior, and when it exceeds 50% by mass, the heat resistance of the cured film may be inferior. On the other hand, when the content is within the particularly preferable range, it is advantageous in that the toughness and heat resistance of the cured film are improved.

-Curing accelerator-
The curing accelerator is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include organic phosphine compounds, imidazole compounds, amine adduct compounds, and tertiary amine compounds.
Examples of the organic phosphine compound include triphenylphosphine. A commercially available product can be used as the organic phosphine compound. Examples of commercially available organic phosphine compounds include TPP, TPP-K, TPP-S, and TPTP-S (all manufactured by Hokuko Chemical Co., Ltd.).
Examples of the imidazole compound include 2-ethyl 4-methylimidazole. A commercial item can be used for the imidazole compound. Examples of commercially available products of the imidazole compound include Curezol 2MZ, 2E4MZ, C11Z, C11Z-CN, C11Z-CNS, C11Z-A, 2MZ-OK, 2MA-OK, and 2PHZ (both manufactured by Shikoku Chemical Industries). Etc.
A commercial item can be used as said amine adduct compound. Examples of commercially available amine adduct compounds include NOVACURE (Asahi Kasei Kogyo Co., Ltd.), Fuji Cure (Fuji Kasei Kogyo Co., Ltd.), and the like.
Examples of the tertiary amine compound include DBU (1,4-diazabicyclo [5,4,0] unde-7-ene).
The content of the curing accelerator is not particularly limited and may be appropriately selected depending on the intended purpose, but is 0.2% by mass to 20% by mass with respect to the nonvolatile content of the thermosetting composition. preferable.

-Other resins-
There is no restriction | limiting in particular as said other resin, According to the objective, it can select suitably, For example, block isocyanate resin, xylene resin, a radical generator, polymeric resin, etc. are mentioned.

-Additive-
There is no restriction | limiting in particular as said additive, According to the objective, it can select suitably, For example, an organic filler, a thickener, an antifoamer, a leveling agent, an adhesiveness imparting agent, a coloring agent etc. are mentioned.
Examples of the organic filler include silicon powder, nylon powder, and fluorine powder.
Examples of the thickener include olben and benton.
Examples of the antifoaming agent and leveling agent include silicone-based, fluorine-based, and polymer-based antifoaming agents and leveling agents.
Examples of the adhesion-imparting agent include imidazole-based, thiazole-based, and triazole-based silane coupling agents.
Examples of the colorant include phthalocyanine / blue, phthalocyanine / green, iodin / green, disazo yellow, and carbon black.

The thermosetting composition can be applied on a circuit board or a conductor circuit layer to form an insulating layer of a multilayer printed wiring board. It is preferably used for formation.

(Adhesive film)
The adhesive film of the present invention has a support and a thermosetting composition layer formed from the thermosetting composition of the present invention on the support, and further includes other layers as necessary. Have.

<Support>
There is no restriction | limiting in particular as a material of the said support body, According to the objective, it can select suitably, For example, polyolefin, polyester, a polycarbonate, a polyimide, a release paper, metal foil etc. are mentioned.
Examples of the polyolefin include polyethylene, polypropylene, and polyvinyl chloride.
Examples of the polyester include polyethylene terephthalate and polyethylene naphthalate.
Examples of the metal foil include copper foil and aluminum foil.

There is no restriction | limiting in particular as a shape of the said support body, According to the objective, it can select suitably, For example, a film form is mentioned.
The average thickness of the film-like support is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 4 μm to 300 μm, more preferably 5 μm to 175 μm.

The support may be subjected to mat treatment, corona treatment, mold release treatment, and the like.

<Thermosetting composition layer>
The said thermosetting composition layer is a layer formed from the said thermosetting composition of this invention on the said support body.

The thermosetting composition layer is softened under the lamination temperature condition (usually 70 ° C. to 140 ° C.) in the vacuum laminating method, and laminated (attached) to the circuit board, and at the same time, via holes or through holes existing in the circuit board It is preferable that the resin exhibits fluidity (resin flow) that can be filled with resin. The diameter of the through hole of the multilayer printed wiring board is usually 0.1 mm to 0.5 mm, and the depth is usually 0.1 mm to 1.2 mm. Usually, it is preferable that the resin can be filled in this range. In addition, when laminating the said thermosetting composition layer on both surfaces of a circuit board, what is necessary is just to fill 1/2 of a through hole. Such physical properties can be characterized by a temperature-melt viscosity curve obtained by measuring dynamic viscoelasticity of the thermosetting composition.

The average thickness of the thermosetting composition layer is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably equal to or greater than the average thickness of the conductor circuit layer of the multilayer printed wiring board. Since the average thickness of the conductor circuit layer is usually in the range of 5 μm to 70 μm, the average thickness of the thermosetting composition layer is preferably 10 μm to 100 μm.

There is no restriction | limiting in particular as a formation method of the said thermosetting composition layer, According to the objective, it can select suitably, For example, the said thermosetting composition of this invention is organic on the said support body. Examples include a method in which a coating solution dissolved or dispersed in a solvent is prepared, and the coating solution is directly applied and dried.

The organic solvent is not particularly limited and may be appropriately selected depending on the intended purpose. For example, alcohols, ketones, esters, aromatic hydrocarbons, halogenated hydrocarbons, ethers, dimethylformamide Dimethylacetamide, dimethylsulfoxide, sulfolane and the like.
Examples of the alcohols include methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, and n-hexanol.
Examples of the ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diisobutyl ketone and the like.
Examples of the esters include ethyl acetate, butyl acetate, n-amyl acetate, methyl sulfate, ethyl propionate, dimethyl phthalate, ethyl benzoate, and methoxypropyl acetate.
Examples of the aromatic hydrocarbons include toluene, xylene, benzene, ethylbenzene and the like.
Examples of the halogenated hydrocarbons include carbon tetrachloride, trichloroethylene, chloroform, 1,1,1-trichloroethane, methylene chloride, and monochlorobenzene.
Examples of the ethers include tetrahydrofuran, diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 1-methoxy-2-propanol, and the like.
These may be used individually by 1 type and may use 2 or more types together.

The nonvolatile concentration of the coating solution is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 10% by mass to 90% by mass, and more preferably 15% by mass to 50% by mass.

The application method is not particularly limited and may be appropriately selected depending on the intended purpose. For example, using a spin coater, slit spin coater, roll coater, die coater, curtain coater, etc. The method of apply | coating is mentioned.
The drying conditions are not particularly limited and may be appropriately selected depending on the purpose. The drying conditions vary depending on each component, the type of solvent, the use ratio, and the like, but are usually 60 ° C. to 110 ° C. for 30 seconds. About 15 minutes.

The thermosetting composition layer formed on the support is preferably formed so that the area of the layer is smaller than the area of the support.

<Other layers>
Examples of the other layers include a protective layer.

-Protective layer-
By protecting the thermosetting composition layer with the protective layer, it is possible to prevent the adhesion of dust, the adhesion of dirt, and the prevention of scratches.
The protective layer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the protective layer is made of the same material as that described in the description of the support, silicone paper, polyethylene, and polypropylene laminated paper. And polytetrafluoroethylene sheet.
The average thickness of the protective layer is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 1 μm to 70 μm.

The adhesive film can be wound and stored in a roll.

The adhesive film can be suitably used as an adhesive film used for multilayer printed wiring boards.

(Multilayer printed wiring board)
The multilayer printed wiring board of the present invention has at least an insulating layer formed of a cured product of the thermosetting composition of the present invention, and further includes other members such as a circuit board and a conductor circuit layer as necessary. Have.

<Insulating layer>
The insulating layer is formed of a cured product of the thermosetting composition of the present invention.

The average thickness of the insulating layer is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably equal to or greater than the average thickness of the conductor circuit layer. Since the average thickness of the conductor circuit layer is usually in the range of 5 μm to 70 μm, the average thickness of the insulating layer is preferably 10 μm to 100 μm.

The method for forming the insulating layer is not particularly limited and may be appropriately selected depending on the purpose.For example, the thermosetting composition is applied onto the circuit board or the conductor circuit layer, A method of forming a cured product by heating (a method of applying), and the adhesive film of the present invention so that the thermosetting composition layer of the adhesive film is in contact with the circuit board or the conductor circuit layer. In addition, a method of laminating (lamination) on the circuit board or the conductor circuit layer and heating to form a cured product (laminating method) may be used.

The coating method is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a spin coater, a slit spin coater, a roll coater, a die coater, and a curtain coater.

The laminating conditions in the laminating method are not particularly limited and may be appropriately selected depending on the intended purpose. The pressure bonding temperature (laminating temperature) is preferably 70 ° C. to 140 ° C. The crimping ^{pressure, 1kgf / cm 2 ~ 11kgf /} cm 2 (9.8 × 10 4 N / m 2 ~ 107.9 × 10 4 N / m 2) is preferred. Moreover, it is preferable to laminate under a reduced pressure of 20 mmHg (26.7 hPa) or less.
A commercially available vacuum laminator can be used for the laminate. Commercially available products of the vacuum laminator include, for example, a vacuum applicator (manufactured by Nichigo Morton), a vacuum pressure laminator (manufactured by Meiki Seisakusho), a roll type dry coater (manufactured by Hitachi Industries), and a vacuum laminator (Hitachi Air). Etc.).
The lamination method may be a batch method or a continuous method using a roll or the like. Further, before the lamination, the adhesive film, the circuit board, and the conductor circuit layer may be heated (preheated) as necessary.

The heating conditions for forming the cured product in the coating method and the laminating method are not particularly limited and can be appropriately selected depending on the purpose. In the heating conditions, the heating temperature is preferably 150 ° C. to 220 ° C., more preferably 160 ° C. to 200 ° C. The heating time is preferably 20 minutes to 180 minutes, more preferably 30 minutes to 120 minutes.

After the insulating layer is formed on the circuit board or the conductor circuit layer, holes are formed in the insulating layer as necessary to form via holes and through holes. There is no restriction | limiting in particular as a method of performing the said drilling, According to the objective, it can select suitably, For example, the method using a drill, a laser, plasma etc. is mentioned. Moreover, it can carry out combining these methods as needed. Among these, the drilling method using a laser is preferable. The laser is preferably a carbon dioxide laser or a YAG laser.

The surface of the insulating layer may be roughened with an oxidizing agent. There is no restriction | limiting in particular as said oxidizing agent, According to the objective, it can select suitably, For example, permanganate (potassium permanganate, sodium permanganate etc.), dichromate, ozone, peroxidation Examples include hydrogen / sulfuric acid and nitric acid. Among these, an alkaline permanganate solution (for example, potassium permanganate, sodium permanganate hydroxide), which is an oxidizing agent generally used for roughening an insulating layer in the production of a multilayer printed wiring board by a built-up method. Sodium aqueous solution) is preferred.

<Circuit board>
There is no restriction | limiting in particular as said circuit board, According to the objective, it can select suitably, For example, a glass epoxy board | substrate, a metal board | substrate, a polyester board | substrate, a polyimide board | substrate, a BT resin board | substrate, a thermosetting type polyphenylene ether board | substrate etc. are mentioned. It is done.
As for the said circuit board, the said insulating layer and the said conductor circuit layer may be formed in the single side | surface, and may be formed in both surfaces.

<Conductor circuit layer>
The conductor circuit layer is not particularly limited as long as it is a layer having a circuit formed of a conductor, and can be appropriately selected according to the purpose.
There is no restriction | limiting in particular as said conductor, According to the objective, it can select suitably, For example, copper, nickel, gold | metal | money, titanium, platinum, tungsten, aluminum, cobalt, chromium, silver, lead, zinc, nickel iron alloy Etc.
The method for forming the conductor circuit layer is not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include a subtractive method and a semi-additive method. Specifically, the conductor circuit layer may be formed on the insulating layer. Examples thereof include a method combining electroless plating and electrolytic plating, a method in which a plating resist having a pattern opposite to that of the conductor circuit layer is formed, and forming only by electroless plating, and a sputtering method.
After the conductor circuit layer is formed, the peel strength of the conductor circuit layer can be improved and stabilized by annealing at 150 to 200 ° C. for 20 to 90 minutes.

The structure of the multilayer printed wiring board is not particularly limited and may be appropriately selected depending on the purpose. For example, the insulating layer and the conductor circuit layer are alternately arranged on one side or both sides of the circuit board. A stacked structure is exemplified.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples. In the following examples, unless otherwise specified, “part” and “%” mean “part by mass” and “% by mass”, respectively.

(Synthesis Example 1)
<Synthesis of Compound T-1>
To a 2,000 mL 3-neck flask equipped with a reflux tube and a thermometer, 250 g of N-methylpyrrolidone and 49.5 g of 3,5-diamino-1,2,4-triazole (manufactured by Degussa) were added. Under stirring, 80 g of N-methylpyrrolidone and 152.2 g of tetrahydrophthalic anhydride (Rikazide TH, manufactured by Shin Nippon Chemical Co., Ltd.) were added dropwise over 2 hours. Thereafter, the mixture was stirred at 40 ° C. for 1 hour and then reacted at 100 ° C. for 12 hours. After cooling to room temperature, the reaction solution was poured into 1.2 L of ion-exchanged water with strong stirring to crystallize the desired product. Washing with isopropanol / hexane (2/8 (mass ratio)), filtering and drying, 121.1 g of compound T-1 having the following structure was obtained.

(Synthesis Example 2)
<Synthesis of Compound T-2>
To a 2,000 mL three-necked flask equipped with a reflux tube and a thermometer, 250 g of N-methylpyrrolidone and 42.0 g of 3-amino-1,2,4-triazole (manufactured by Junsei Chemical Co., Ltd.) were added. Under stirring, 80 g of N-methylpyrrolidone and 152.2 g of 5-methacryloyloxyethyl-trimellitic acid-1,2-anhydride (manufactured by Wako Pure Chemical Industries, Ltd.) were added dropwise over 2 hours. Thereafter, the mixture was stirred at 40 ° C. for 1 hour and then reacted at 100 ° C. for 5 hours. After cooling to room temperature, the reaction solution was poured into 1.2 L of ion-exchanged water with strong stirring to crystallize the desired product. By washing with isopropanol / methanol (22/78 (mass ratio)), filtering and drying, 112.3 g of compound T-2 having the following structure was obtained.

(Synthesis Example 3)
<Synthesis of Compound T-3>
In a 2,000 mL three-necked flask equipped with a reflux tube and a thermometer, 120 g of tetrahydrofuran, 70 g of N-methylpyrrolidone, 49.5 g of 3,5-diamino-1,2,4-triazole (manufactured by Degussa), and 1.8 g of 2,4-di-tert-butyl-4-methylphenol (PN-01, manufactured by Ouchi Shinsei Chemical Co., Ltd.) was added. Under stirring, 80 g of tetrahydrofuran and 141.1 g of 2-isocyanatoethyl acrylate (Karenz AOI, manufactured by Showa Denko KK) were added dropwise over 2 hours. Then, it was made to react at 40 degreeC for 20 hours. After cooling to room temperature, the reaction solution was poured into 2 L of ion-exchanged water under strong stirring to crystallize the target product. By washing with methanol, filtering and drying, 165.1 g of compound T-3 having the following structure was obtained.

(Synthesis Example 4)
<Synthesis of Compound T-4>
In a 1,000 mL three-necked flask equipped with a reflux tube and a thermometer, 250 g of t-butyl methyl ketone, 34.5 g of 1,2,4-triazole (manufactured by Junsei Chemical Co., Ltd.), dicyclopentanyl dimethanol dimer Add 145.7 g of acrylate (A-DCP, Shin-Nakamura Chemical Co., Ltd.) and 1.9 g of 2,4-di-t-butyl-4-methylphenol (PN-01, Ouchi Shinsei Chemical Co., Ltd.) It was. After stirring at 40 ° C. for 1 hour, the reaction was carried out at 80 ° C. for 52 hours. After cooling to room temperature, the organic solvent was removed by concentration under reduced pressure to obtain 178 g of compound T-4 having the following structure.

Example 1
<Preparation of multilayer printed wiring board 1>
-Preparation of thermosetting composition 1-
20 parts by mass of liquid bisphenol F type epoxy resin (YDF-170, epoxy equivalent 172 g / eq, manufactured by Nippon Steel Chemical Co., Ltd.) and naphthalene type tetrafunctional epoxy resin (EXA-4700, epoxy equivalent 163 g / eq, manufactured by DIC) 12 parts by mass was added to 20 parts by mass of cyclohexanone with stirring and dissolved by heating. Thereto, 3.5 parts by mass of the compound (T-1) synthesized in Synthesis Example 1, a triazine structure-containing phenol novolac resin MEK varnish (Phenolite LA-7052, manufactured by DIC, non-volatile content 60% by mass, non-volatile phenol 25 parts by mass of hydroxyl group equivalent 120), 20 parts by mass of phenoxy resin varnish (FX293, Nippon Steel Chemical Co., Ltd., nonvolatile content 40% by mass), and 60 parts by mass of spherical silica (average particle size 0.5 μm, aminosilane treatment) The thermosetting composition 1 was prepared by addition.

-Production of adhesive film 1-
On a polyethylene terephthalate film (thickness 38 μm, hereinafter abbreviated as PET film), the thermosetting composition 1 is applied using a die coater so that the average thickness after drying is 50 μm, and dried at 80 ° C. for 15 minutes. (A residual solvent amount of about 1% by mass), a thermosetting composition layer was formed. Next, an adhesive film 1 was produced by winding up a 15 μm-thick polypropylene film as a protective layer on the formed thermosetting composition layer in a roll shape.

-Fabrication of multilayer printed wiring board 1-
A circuit board was prepared using a FR4 double-sided copper-clad laminate (copper foil thickness 18 μm) having a thickness of 0.3 mm (with a through hole having a diameter of 0.2 mm). After the polypropylene film of the produced adhesive film 1 was peeled off, the thermosetting composition layer was in contact with the circuit surface of the circuit board, and a temperature of 110 ° C., a pressure of 7 kgf / cm ² , and an atmospheric pressure of 5 mmHg (1) was applied by a vacuum laminator. .33 hPa) The adhesive film 1 was laminated on both sides of the circuit board under the following conditions. Next, the PET film of the adhesive film 1 was peeled off and cured by heating at 180 ° C. for 30 minutes to form an insulating layer. After that, drilling with a laser to form a via hole, then roughening the surface of the insulating layer with an alkaline oxidizer of permanganate, electroless plating and electrolytic plating to form a conductor circuit layer according to the subtractive method A multilayer printed wiring board was obtained. Thereafter, an annealing treatment was further performed at 180 ° C. for 30 minutes. The thickness of the conductor plating of the obtained conductor circuit layer was about 30 μm, and the through hole was completely filled with resin.

<Evaluation>
The following evaluation was performed. The results are shown in Table 1.
-Insulation-
--- Fabrication of printed wiring board for evaluation ---
One side of 0.3 mm thick FR4 double-sided copper clad laminate (copper foil thickness 18 μm) is etched, the line width / space width is 50 μm / 50 μm, and the lines are not in contact with each other, facing each other A circuit board on which comb-shaped electrodes on the same surface were formed was produced. After the polypropylene film of the adhesive film 1 is peeled off, the thermosetting composition layer is brought into contact with the comb-shaped electrode of the circuit board, and a temperature of 110 ° C., a pressure of 7 kgf / cm ² , and a pressure of 5 mmHg (1. 33 hPa) The adhesive film 1 was laminated on the circuit board under the following conditions. Next, the PET film of the adhesive film 1 was peeled off and cured by heating at 180 ° C. for 30 minutes, an insulating layer was formed, and a printed wiring board for evaluation was produced.
--- Insulation evaluation ---
After connecting the polytetrafluoroethylene shield wires to the comb electrodes by Sn / Pb solder so that a voltage is applied between the comb electrodes formed on the evaluation printed wiring board, With the voltage of 5 V applied, the printed wiring board for evaluation was left in a super accelerated high temperature and high humidity test (HAST) bath at 130 ° C. and 85% RH for 200 hours. Thereafter, the degree of migration of the insulating layer of the printed wiring board for evaluation was observed with a 100-fold metal microscope and evaluated according to the following evaluation criteria.
[Evaluation criteria]
◎: The occurrence of migration is not confirmed and the insulation is excellent. ○: The occurrence of migration is slightly confirmed on copper, but the insulation is good. ○ △: The migration is slightly confirmed in the insulating layer. , Insulation is slightly good △: migration is confirmed, insulation is slightly inferior ×: short between electrodes, insulation is inferior

-Desmear property-
The protective layer of the adhesive film is peeled off, and the adhesive film is subjected to FR4 double-sided copper-clad laminate using a vacuum laminator (MVLP-500) manufactured by Meiki Seisakusho at a pressure of 5 mmHg or less, a temperature of 100 ° C., and a pressure of 7 kgf / cm ^2. Laminated on both sides simultaneously. Further, hot pressing with a SUS end plate was performed continuously under conditions of a temperature of 100 ° C. and a pressure of 5 kgf / cm ² . And PET film was peeled and the thermosetting process was performed for 30 minutes at 180 degreeC. Next, assuming desmear treatment, roughening solution (Swelling Dip Securigans P (swelling treatment solution), Concentrate Compact CP (oxidation treatment solution), reduction, made by Atotech Japan Co., which is an oxidizer solution Solution Securigant P (neutralization solution)) is used to swell the laminate at 60 ° C for 5 minutes, oxidation treatment at 80 ° C for 20 minutes, and neutralization treatment at 40 ° C for 5 minutes in this order. I went there.
The resulting cured film was visually observed for bulging and peeling to evaluate desmearability. The evaluation criteria are as follows.
[Evaluation criteria]
○: There is no unevenness on the sparse surface, no floating, peeling or swelling occurs, and the desmear resistance is excellent.
Δ: Despite some unevenness on the roughened surface, no floatation, peeling or swelling occurs, and desmear resistance is good.
X: Floating, peeling and swelling occur and inferior in desmear resistance.

-Plating-resistant adhesion-
--- Fabrication of printed wiring board for evaluation ---
A circuit board was prepared using a FR4 double-sided copper-clad laminate (copper foil thickness 18 μm) having a thickness of 0.3 mm (with a through hole having a diameter of 0.2 mm). After the polypropylene film of the adhesive film 1 is peeled off, the thermosetting composition layer is in contact with the circuit surface of the circuit board, and is heated by a vacuum laminator at a temperature of 110 ° C., a pressure of 7 kgf / cm ² , and an atmospheric pressure of 5 mmHg (1.33 hPa). ) The adhesive film 1 was laminated on both sides of the circuit board under the following conditions. Next, the PET film of the adhesive film 1 was peeled off and cured by heating at 180 ° C. for 30 minutes, an insulating layer was formed, and a printed wiring board for evaluation was produced.
--- Evaluation of anti-plating adhesion ---
The formed insulating layer was degreased to roughen the surface, and then palladium sulfate was added to add a catalyst. Next, after immersing the printed wiring board for evaluation in a nickel sulfate / dilute sulfuric acid solution at 70 ° C. for 40 minutes for plating treatment, the insulation layer was turned up and peeled off visually, based on the following criteria: Then, the plating resistance was evaluated.
[Evaluation criteria]
◎: Insulation layer is not turned over and peeled off, and extremely excellent in plating-resistant adhesion ○: Part of the insulating layer is discolored, but there is no practical problem and excellent in plating-resistant adhesion ○ △: Insulating layer Discoloration, but no problem in practical use, good adhesion resistance against plating △: Insulation layer is turned over, poor adhesion to plating area ×: Floating (peeling) is observed in insulation layer, anti-plating Very poor adhesion

(Example 2)
A thermosetting composition, an adhesive film, and a multilayer printed wiring board were produced in the same manner as in Example 1 except that the compound T-1 was replaced with the compound T-2 in Example 1.
Evaluation similar to Example 1 was performed. The results are shown in Table 1.

(Example 3)
A thermosetting composition, an adhesive film, and a multilayer printed wiring board were produced in the same manner as in Example 1 except that the compound T-1 was replaced with the compound T-3 in Example 1.
Evaluation similar to Example 1 was performed. The results are shown in Table 1.

Example 4
A thermosetting composition, an adhesive film, and a multilayer printed wiring board were produced in the same manner as in Example 1 except that the compound T-1 was replaced with the compound T-4 in Example 1.
Evaluation similar to Example 1 was performed. The results are shown in Table 1.

(Example 5)
In Example 1, except that the blending amount was changed so that the content of T-1 (content with respect to the nonvolatile content of the obtained thermosetting composition) was 3.0% by mass to 0.5% by mass. In the same manner as in Example 1, a thermosetting composition, an adhesive film, and a multilayer printed wiring board were produced.
Evaluation similar to Example 1 was performed. The results are shown in Table 1.

(Example 6)
In Example 1, except that the blending amount was changed so that the content of T-1 (content with respect to the nonvolatile content of the obtained thermosetting composition) was 3.0% by mass to 1.7% by mass. In the same manner as in Example 1, a thermosetting composition, an adhesive film, and a multilayer printed wiring board were produced.
Evaluation similar to Example 1 was performed. The results are shown in Table 1.

(Example 7)
In Example 1, except that the blending amount was changed so that the content of T-1 (content with respect to the nonvolatile content of the obtained thermosetting composition) was 3.0% by mass to 15.0% by mass. In the same manner as in Example 1, a thermosetting composition, an adhesive film, and a multilayer printed wiring board were produced.
Evaluation similar to Example 1 was performed. The results are shown in Table 1.

(Example 8)
In Example 1, except that liquid bisphenol F type epoxy resin (YDF-170) and naphthalene type tetrafunctional epoxy resin (EXA-4700) were replaced with trifunctional epoxy resin (VG-3101, manufactured by Printec). In the same manner as in Example 1, a thermosetting composition, an adhesive film, and a multilayer printed wiring board were produced.
Evaluation similar to Example 1 was performed. The results are shown in Table 1.

Example 9
The thermosetting composition was the same as in Example 1, except that the naphthalene type tetrafunctional epoxy resin (EXA-4700) was replaced with a cresol novolac type epoxy resin (N-697, manufactured by DIC) in Example 1. An adhesive film and a multilayer printed wiring board were produced.
Evaluation similar to Example 1 was performed. The results are shown in Table 1.

(Comparative Example 1)
In Example 1, the thermosetting composition was the same as Example 1 except that the liquid bisphenol F type epoxy resin, naphthalene type tetrafunctional epoxy resin, and compound T-1 were not added to the thermosetting composition. Articles, adhesive films, and multilayer printed wiring boards were produced.
Evaluation similar to Example 1 was performed. The results are shown in Table 1.

(Comparative Example 2)
A thermosetting composition, an adhesive film, and a multilayer printed wiring board were produced in the same manner as in Example 1 except that Compound T-1 was not added.
Evaluation similar to Example 1 was performed. The results are shown in Table 1.

(Comparative Example 3)
In Example 1, except that the compound T-1 was replaced by the following compound TZ (1,2,4-triazole), the thermosetting composition, the adhesive film, and the multilayer print were the same as in Example 1. A wiring board was produced.
Evaluation similar to Example 1 was performed. The results are shown in Table 1.

In Table 1, the content of the triazole compound indicates the content (% by mass) relative to the nonvolatile content of the thermosetting composition.

As an aspect of this invention, the following aspects are mentioned, for example.
<1> An epoxy resin having two or more epoxy groups in one molecule, a compound having a triazole ring and at least one of a group having a radically polymerizable double bond and a group capable of reacting with an epoxy group, It is a thermosetting composition characterized by containing.
<2> The thermosetting composition according to <1>, further including a phenol-based curing agent.
<3> The thermosetting composition according to any one of <1> to <2>, further including an inorganic filler.
<4> The above <1>, wherein the compound having a triazole ring and at least one of a group having a radically polymerizable double bond and a group capable of reacting with an epoxy group is a compound represented by the following general formula (I): To <3>.

However, in said general formula (I), X represents a triazole ring. Y represents an organic group having at least one of a group having a double bond capable of radical polymerization and a group capable of reacting with an epoxy group. n represents an integer of 1 to 3. When n is 2 to 3, Y may be the same or different.
<5> The thermosetting composition according to <4>, wherein Y in the general formula (I) is a group represented by the following general formula (II).

In the general formula (II), Y ₁ represents an m + 1 valent organic group having 2 to 25 carbon atoms. Z ₁ represents any of a carboxyl group, an acryloyloxy group, and a methacryloyloxy group. m represents an integer of 1 to 2. When m is 2, Z ₁ may be the same or different.
<6> The thermosetting composition according to any one of <1> to <5>, further including at least one selected from a phenoxy resin, a polyvinyl acetal resin, a polyamide resin, and a polyamideimide resin.
<7> Adhesive comprising a support and a thermosetting composition layer formed from the thermosetting composition according to any one of <1> to <6> on the support. It is a film.
<8> A multilayer printed wiring board comprising an insulating layer formed of a cured product of the thermosetting composition according to any one of <1> to <6>.

Since the thermosetting composition and adhesive film of the present invention are excellent in insulating properties, desmear properties, and plating-resistant adhesion, they can be suitably used for multilayer printed wiring boards.
The multilayer printed wiring board of the present invention is excellent in insulation, desmearing properties, and plating-resistant adhesion, and therefore can be suitably used for a build-up type multilayer printed wiring board.

Claims (8)

1. Containing an epoxy resin having two or more epoxy groups in one molecule and a compound having a triazole ring and at least one of a group having a radically polymerizable double bond and a group capable of reacting with an epoxy group A thermosetting composition characterized by the above.
2. Furthermore, the thermosetting composition of Claim 1 containing a phenol type hardening | curing agent.
3. The thermosetting composition according to claim 1, further comprising an inorganic filler.
4. The compound having a triazole ring and at least one of a group having a radically polymerizable double bond and a group capable of reacting with an epoxy group is a compound represented by the following general formula (I): A thermosetting composition according to any one of the above.
   

   

   However, in said general formula (I), X represents a triazole ring. Y represents an organic group having at least one of a group having a double bond capable of radical polymerization and a group capable of reacting with an epoxy group. n represents an integer of 1 to 3. When n is 2 to 3, Y may be the same or different.
5. The thermosetting composition according to claim 4, wherein Y in the general formula (I) is a group represented by the following general formula (II).
   

   

   In the general formula (II), Y ₁ represents an m + 1 valent organic group having 2 to 25 carbon atoms. Z ₁ represents any of a carboxyl group, an acryloyloxy group, and a methacryloyloxy group. m represents an integer of 1 to 2. When m is 2, Z ₁ may be the same or different.
6. The thermosetting composition according to any one of claims 1 to 5, further comprising at least one selected from a phenoxy resin, a polyvinyl acetal resin, a polyamide resin, and a polyamideimide resin.
7. An adhesive film comprising: a support; and a thermosetting composition layer formed from the thermosetting composition according to any one of claims 1 to 6 on the support.
8. A multilayer printed wiring board comprising an insulating layer formed of a cured product of the thermosetting composition according to claim 1.