KR102415755B1 - Thermosetting resin composition, dry film, cured product and printed wiring board - Google Patents

Abstract

Provided are a thermosetting resin composition, a dry film, a cured product, and a printed wiring board having better performance than before. (A) It is a thermosetting resin composition containing a bisphenol E-type epoxy resin, (B) any one or both of a hardening|curing agent and a hardening accelerator, and (C) a filler. It is a dry film which has a resin layer obtained by apply|coating and drying the said thermosetting resin composition on a film, hardened|cured material obtained by hardening this, and a printed wiring board which has this hardened|cured material.

Description

Thermosetting resin composition, dry film, cured product and printed wiring board

The present invention relates to a thermosetting resin composition (hereinafter simply referred to as “composition”), a dry film, a cured product, and a printed wiring board, and more particularly, a thermosetting resin composition having better performance than before for the production of a printed wiring board, a dry It relates to a film, a hardened|cured material, and a printed wiring board.

In recent years, as a manufacturing method of a multilayer printed wiring board, the manufacturing technique of the build-up system which stacks up the resin insulating layer and the conductor layer alternately on the conductor layer of an inner-layer circuit board is attracting attention. For example, a method of manufacturing a multilayer printed wiring board in which an epoxy resin composition is applied to a circuit-formed inner-layer circuit board, heat-cured, an uneven roughened surface is formed on the surface with a roughening agent, and a conductor layer is formed by plating. It has been proposed (see Patent Document 1 and Patent Document 2). In addition, after laminating an adhesive sheet of an epoxy resin composition on a circuit-formed inner-layer circuit board, heat-curing, forming an uneven roughened surface on the surface with a roughening agent, and forming a conductor layer by plating Method of manufacturing a multilayer printed wiring board This has been proposed (refer to Patent Document 3).

Here, an example of the formation method of the layer structure of the multilayer printed wiring board by the conventional build-up method is demonstrated, referring FIG. First, an outer conductor pattern 108 is formed on both surfaces of a laminated substrate X on which an inner conductor pattern 103 and a resin insulating layer 104 are previously formed on both surfaces of the insulating substrate 101, and an epoxy resin composition or the like is formed thereon. An insulating resin composition is applied by coating or the like, and cured by heating to form the resin insulating layer 109 . Subsequently, after the through-hole holes 121 and the like are appropriately provided, a conductor layer is formed on the surface of the resin insulating layer 109 by electroless plating or the like, and then, according to a conventional method, a predetermined circuit pattern is applied to the conductor layer. formed to form the outermost conductor pattern 110 . In the drawing, reference numeral 103a denotes a connection part, 120 denotes a through hole, and 122 denotes a connection part.

As one of the methods of forming a resin insulating layer (hereinafter also referred to as "interlayer insulating layer") provided between layers in a multilayer printed wiring board, as described in Patent Document 3, a thermosetting resin composition such as an epoxy resin composition The method of forming by thermosetting the dry film which has a resin layer obtained by coating-drying on a film after lamination is used is used. As a resin composition applied to manufacture of such a multilayer printed wiring board, what used together the some epoxy resin containing a bisphenol A epoxy resin and a bisphenol F epoxy resin is disclosed by patent document 4, for example.

On the other hand, in a multilayer printed wiring board, development of the composition for permanent hole embedding for filling in recesses, such as a through hole and a via hole, and a through hole is desired. Generally, as a composition for permanent hole embedding of a printed wiring board, a thermosetting epoxy resin composition is widely used, and the permanent hole embedding process of a printed wiring board using such a resin composition is usually carried out by injecting an epoxy resin composition into the hole part of a printed wiring board. A step of filling the porcelain, a step of pre-curing the filled composition to a polished state, a step of polishing/removing a portion protruding from the surface of the hole of the pre-cured resin composition, and a pre-cured resin composition It is performed by the process of further heating and main hardening. As an epoxy resin composition for hole filling of a printed wiring board, the thing which does not contain a solvent substantially is used, for example, there exist some which are disclosed by patent documents 5 and 6.

Japanese Patent Laid-Open No. 7-304931 (claims) Japanese Patent Laid-Open No. 7-304933 (claims) Japanese Patent Laid-Open No. 2010-1403 (claims) Japanese Patent Laid-Open No. 2014-28880 (claims) Japanese Patent Laid-Open No. 10-075027 (claims) Japanese Patent Laid-Open No. 11-222549 (claims)

As described above, the epoxy resin composition is used for various purposes. However, in the composition containing the epoxy resin used conventionally, when it was set as the form of a dry film, there existed a problem that the softness|flexibility of a dry film fell. Moreover, the hardened|cured material obtained from the composition containing the liquid epoxy resin used conventionally had a comparatively low glass transition temperature, and also had the problem that a void was easy to generate|occur|produce.

Then, the objective of this invention is to solve the said subject, and to provide the thermosetting resin composition, dry film, hardened|cured material, and a printed wiring board provided with the performance more excellent than before.

As a result of earnest examination, these inventors discovered that the said subject could be solved by using the bisphenol E-type epoxy resin which was not used conventionally as an epoxy resin, and came to complete this invention.

That is, the thermosetting resin composition of this invention contains (A) a bisphenol E epoxy resin, (B) either or both of a hardening|curing agent and a hardening accelerator, and (C) a filler, It is characterized by the above-mentioned.

The composition of this invention is used suitably for manufacture of a printed wiring board, and is especially used suitably for any one of an interlayer insulating material of a printed wiring board, a soldering resist, a coverlay, or a hole filling application. The composition of this invention can be made into the thing which does not contain a solvent depending on a use, and can also be set as the thing which does not contain a semi-solid epoxy resin and a solid epoxy resin. In addition, the composition of the present invention may contain at least any one of a phenol resin, an active ester resin and a cyanate ester resin as the curing agent, depending on the use, and a bisphenol A type epoxy resin and a bisphenol F type epoxy resin It may be made to include more. Moreover, in the composition of this invention, it is preferable that the said (C) filler contains any one or both of a calcium carbonate and a silica.

The dry film of this invention has a resin layer obtained by apply|coating and drying the said thermosetting resin composition of this invention on a film, It is characterized by the above-mentioned. In the dry film of this invention, it is preferable that the residual solvent amount of the said resin layer is less than 1 mass % based on the resin layer whole quantity containing a solvent.

The cured product of the present invention is obtained by curing the thermosetting resin composition of the present invention or the resin layer of the dry film of the present invention.

The printed wiring board of this invention has the said hardened|cured material of this invention, It is characterized by the above-mentioned.

According to the present invention, the dry film has good flexibility, the glass transition temperature of the cured product is higher than that of a cured product obtained from a conventionally used liquid epoxy resin-containing composition, and a thermosetting resin composition, dry film, cured product, and print that is less prone to voiding. It became possible to realize a wiring board.

BRIEF DESCRIPTION OF THE DRAWINGS It is a partial sectional drawing which shows schematic structure of the multilayer printed wiring board produced by the conventional build-up method.
It is a schematic side view which shows the two test tubes used for liquid phase determination of an epoxy resin.
It is a schematic sectional drawing which shows an example of a part of the manufacturing process of the printed wiring board of this invention.
It is a schematic sectional drawing which shows an example of the subsequent process of the manufacturing process of the printed wiring board of this invention shown in FIG.
It is a schematic sectional drawing which shows the other example of the manufacturing method of the printed wiring board of this invention.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described in detail.

In addition, in this specification, (meth)acrylate is a term which generically names an acrylate, a methacrylate, and a mixture thereof, and it is the same also about other similar expression.

The thermosetting resin composition of this invention has a characteristic in the point containing (A) a bisphenol E-type epoxy resin, any one or both of (B) a hardening|curing agent and a hardening accelerator, and (C) a filler. By using the bisphenol E-type epoxy resin which has not been used conventionally as an epoxy resin, compared with the case where conventional general-purpose various epoxy resins were used, it became possible to set it as the thermosetting resin composition provided with the more outstanding performance. The thermosetting resin composition of this invention is useful for manufacture of a printed wiring board, Especially in the interlayer insulating material of a printed wiring board, a soldering resist, and a hole filling use, it is used suitably.

Since the composition of this invention is excellent in storage stability, it can be set as the one-component type which mixed all the components. Of course, the composition of this invention is good also as a two-component type which divided the said (A) component and said (B).

[(A) Bisphenol E Epoxy Resin]

Bisphenol E-type epoxy resins have a skeleton represented by the following structural formula, are liquid at room temperature, and have low viscosity and high heat resistance compared to bisphenol A-type epoxy resins and bisphenol F-type epoxy resins having a similar structure. have That is, while the bisphenol A epoxy resin is equivalent to the E-type in terms of heat resistance, the viscosity is high, and the bisphenol F-type epoxy resin has a relatively low viscosity, but has a difficult point of low heat resistance, bisphenol E epoxy resin can be said to have the advantages of type A and type F. As a bisphenol E-type epoxy resin, EPOX-MK R710, R1710, etc. made from Co., Ltd. PRINTEC can be used, for example.

For example, when using the resin composition used for an interlayer insulating material and a soldering resist especially as a dry film, in order to maintain the softness|flexibility of a film, it is necessary to use a liquid epoxy resin as a resin component. In addition, in order to improve the curing characteristics of the resin composition, a method of using semi-solid and solid epoxy resins with the amount of liquid epoxy resin used is kept to the necessary minimum is considered, but in the case of using a conventional bisphenol A epoxy resin , the flexibility of the film becomes insufficient, and the problem of powder falling or cracking of the resin arises. On the other hand, when the bisphenol F-type epoxy resin was used, heat resistance was inadequate. Therefore, in order to increase the flexibility when the film has insufficient flexibility, a method of increasing the residual solvent amount of the film has been conventionally used. There was a problem with losing.

On the other hand, in the composition of this invention which used (A) bisphenol E-type epoxy resin as an epoxy resin, a viscosity is lower than when a bisphenol A-type epoxy resin is used, and heat resistance becomes higher than when a bisphenol F-type epoxy resin is used. Moreover, the flexibility of a film equivalent to the case where a bisphenol F-type epoxy resin is used can be acquired. Thereby, since the amount of residual solvent can be reduced, the problem of void generation can be eliminated. In addition, since the dry film can be used also for hole filling applications normally used in the form of a solvent-free liquid resin composition by reducing the residual solvent amount of the dry film and solving the problem of voids, in the production of a printed wiring board, the interlayer It also becomes possible to perform all of an insulating material, a soldering resist, and a hole filling use with 1 type of dry film. That is, although the soldering resist layer was conventionally formed after hole filling, it became possible to perform these in one process simultaneously, and it became possible to obtain the high-quality board|substrate which suppressed the void, aiming at the simplification of a process, and cost reduction.

On the other hand, for example, since a resin composition used for hole filling applications such as through holes is usually used as a liquid resin composition (pore filling ink), a liquid epoxy resin is widely used in order to form a paste without a solvent. . However, bisphenol A type epoxy resin has high viscosity, so sufficient printability is not obtained, bisphenol F type epoxy resin has low heat resistance and is prone to cracking, and aminophenol type epoxy resin has high water absorption and fast curing. Because it is hard, the abrasiveness is poor, the phenol novolac type epoxy resin has high water absorption, and in addition to the high viscosity, sufficient printability is not obtained, and the monofunctional epoxy resin has low heat resistance and is prone to cracking. It wasn't enough.

On the other hand, in the composition of the present invention using (A) bisphenol E-type epoxy resin as the epoxy resin, in addition to being able to achieve both low viscosity and high heat resistance, bubbles are easy to escape during printing and generation of voids is suppressed, and the filler Since high filling is possible, the CTE can be further reduced, and since it has the same flexibility as that of the F-type, it is also excellent in abrasiveness.

Moreover, in the composition of this invention, it turned out that storage stability becomes favorable unexpectedly by the combination of (A) bisphenol E-type epoxy resin, bisphenol A-type epoxy resin, and bisphenol F-type epoxy resin. Moreover, (A) Tg improves by the combination of a bisphenol E-type epoxy resin and an aminophenol-type epoxy resin, and it becomes the thing excellent in heat resistance. (A) In addition to the bisphenol E type epoxy resin, when using a bisphenol A type epoxy resin and a bisphenol F type epoxy resin, their compounding ratio is bisphenol A type epoxy resin/bisphenol F type epoxy resin (mass ratio) = 0.1 to 10.0 can do.

And in the composition of the hole filling use of this invention, it is preferable not to contain a solvent from a viewpoint of suppressing generation|occurrence|production of a void. Moreover, it is preferable not to contain a semi-solid or solid epoxy resin from a viewpoint of the fillability to a hole part.

[(B) curing agent and curing accelerator]

The composition of the present invention contains either or both of (B) a curing agent and a curing accelerator.

(hardener)

As a hardening|curing agent, a phenol resin, polycarboxylic acid, its acid anhydride, cyanate ester resin, active ester resin, etc. are mentioned. A hardening|curing agent can be used individually by 1 type or in combination of 2 or more type.

Examples of the phenol resin include phenol novolak resin, alkylphenol novolak resin, bisphenol A novolak resin, dicyclopentadiene type phenol resin, Xylok type phenol resin, terpene-modified phenol resin, cresol/naphthol resin, poly Conventionally known ones such as vinyl phenols, phenol/naphthol resins, α-naphthol skeleton-containing phenol resins and triazine-containing cresol novolac resins can be used alone or in combination of two or more.

The polycarboxylic acid and its acid anhydride are a compound having two or more carboxyl groups in one molecule and an acid anhydride thereof, for example, a copolymer of (meth)acrylic acid, a copolymer of maleic anhydride, and a condensate of a dibasic acid In addition to these, resins having a carboxylic acid terminal, such as a carboxylic acid terminal imide resin, are exemplified.

The cyanate ester resin is a compound having two or more cyanate ester groups (-OCN) in one molecule. Any conventionally well-known thing can be used for cyanate ester resin. As cyanate ester resin, for example, phenol novolak type cyanate ester resin, alkylphenol novolak type cyanate ester resin, dicyclopentadiene type cyanate ester resin, bisphenol A type cyanate ester resin, bisphenol F type cyanide Nate ester resin and bisphenol S type|mold cyanate ester resin are mentioned. Moreover, the prepolymer by which a part was triazined may be sufficient.

The active ester resin is a resin having two or more active ester groups in one molecule. The active ester resin can generally be obtained by a condensation reaction of a carboxylic acid compound and a hydroxy compound. Especially, the active ester compound obtained using a phenol compound or a naphthol compound as a hydroxy compound is preferable. Examples of the phenolic compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthalline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p- Cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzo and phenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadienyldiphenol, and phenol novolac.

Moreover, you may use an alicyclic olefin polymer as a hardening|curing agent. As a specific example of the method for producing an alicyclic olefin polymer, (1) a method of polymerizing an alicyclic olefin having a carboxyl group and/or a carboxylic acid anhydride group (hereinafter referred to as “carboxyl group etc.”) together with other monomers as needed , (2) a method of hydrogenating the aromatic ring portion of a (co)polymer obtained by polymerizing an aromatic olefin having a carboxyl group or the like with other monomers if necessary, (3) an alicyclic olefin having no carboxyl group, and a carboxyl group, etc. A method of copolymerizing a monomer having (4) a method of hydrogenating the aromatic ring moiety of a copolymer obtained by copolymerizing an aromatic olefin having no carboxyl group and the like with a monomer having a carboxyl group, etc., (5) an alicyclic having no carboxyl group, etc. A method in which a compound having a carboxyl group or the like is introduced into the olefin polymer by a modification reaction, or (6) a carboxylate group of an alicyclic olefin polymer having a carboxylate ester group obtained as in (1) to (5) above. , for example, a method of converting to a carboxyl group by hydrolysis or the like.

Among the curing agents, phenol novolak resins, active ester resins, and phenol novolak-type polyfunctional cyanate resins are preferable.

The curing agent is (A) the ratio of the epoxy group of the epoxy resin containing the bisphenol E type epoxy resin and the functional group in the curing agent reacting with the epoxy group is functional group/epoxy group (equivalent ratio) of the curing agent = 0.2 to 2.0. It is preferable to combine. By making the functional group/epoxy group (equivalent ratio) of a hardening|curing agent into the said range, roughening of the film surface in a desmear process can be prevented. More preferably, the functional group/epoxy group (equivalent ratio) of the curing agent is 0.2 to 1.5, and more preferably, the functional group/epoxy group (equivalent ratio) of the curing agent is 0.3 to 1.0.

(curing accelerator)

A curing accelerator accelerates a thermosetting reaction, and is used in order to further improve characteristics, such as adhesiveness, chemical-resistance, and heat resistance. As a specific example of such a hardening accelerator, imidazole and its derivative(s); guanamines such as acetoguanamine and benzoguanamine; polyamines such as diaminodiphenylmethane, m-phenylenediamine, m-xylenediamine, diaminodiphenylsulfone, dicyandiamide, urea, urea derivatives, melamine, and polybasic hydrazide; their organic acid salts and/or epoxy adducts; amine complexes of boron trifluoride; triazine derivatives such as ethyldiamino-S-triazine, 2,4-diamino-S-triazine, and 2,4-diamino-6-xylyl-S-triazine; Trimethylamine, triethanolamine, N,N-dimethyloctylamine, N-benzyldimethylamine, pyridine, N-methylmorpholine, hexa(N-methyl)melamine, 2,4,6-tris(dimethylaminophenol), tetra amines such as methylguanidine and m-aminophenol; polyphenols such as polyvinylphenol, polyvinylphenol bromide, phenol novolac, and alkylphenol novolak; organic phosphines such as tributylphosphine, triphenylphosphine, and tris-2-cyanoethylphosphine; phosphonium salts such as tri-n-butyl (2,5-dihydroxyphenyl) phosphonium bromide and hexadecyl tributyl phosphonium chloride; quaternary ammonium salts such as benzyltrimethylammonium chloride and phenyltributylammonium chloride; the polybasic acid anhydride; photocationic polymerization catalysts such as diphenyliodonium tetrafluoroboroate, triphenylsulfonium hexafluoroantimonate, and 2,4,6-triphenylthiopyrylium hexafluorophosphate; styrene-maleic anhydride resin; A conventionally well-known hardening accelerator, such as an equimolar reaction product of phenyl isocyanate and dimethylamine, an equimolar reaction product of organic polyisocyanate, such as tolylene diisocyanate and isophorone diisocyanate, and dimethylamine, a metal catalyst, is mentioned. Among the curing accelerators, phosphonium salts are preferred from the viewpoint of obtaining BHAST tolerance.

Moreover, especially when using the composition of this invention as a liquid resin composition for pore filling, an imidazole derivative is preferable. Specific examples of the imidazole derivative include 2-methylimidazole, 4-methyl-2-ethylimidazole, 2-phenylimidazole, 4-methyl-2-phenylimidazole, 1-benzyl- 2-methylimidazole, 2-ethylimidazole, 2-isopropylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimida sol, 1-cyanoethyl-2-undecylimidazole, etc. are mentioned. Specific examples of commercially available products include imidazoles such as 2E4MZ, C11Z, C17Z, and 2PZ, AZINE compounds of imidazole such as 2MZ-A and 2E4MZ-A, imidazoles such as 2MZ-OK and 2PZ-OK and imidazole hydroxymethyl compounds such as isocyanuric acid salt and brand names 2PHZ and 2P4MHZ (all of the above brand names are manufactured by Shikoku Kasei Kogyo Co., Ltd.).

In addition to imidazole, dicyandiamide and its derivatives, melamine and its derivatives, diaminomaleonitrile and its derivatives, diethylenetriamine, triethylenetetramine, tetramethylenepentamine, bis(hexamethylene)triamine, and triethanol Amines, such as amines, diaminodiphenylmethane, organic acid hydrazide, 1,8-diazabicyclo[5.4.0]undecene-7 (trade name DBU, manufactured by San-Apro Corporation), 3,9-bis( 3-aminopropyl)-2,4,8,10-tetraoxaspiro[5.5]undecane (trade name ATU, manufactured by Ajinomoto Co., Ltd.), or triphenylphosphine, tricyclohexylphosphine, tributylphosphine; Organic phosphine compounds, such as methyldiphenylphosphine, etc. can be used individually or in combination of 2 or more types. However, when aromatic amines are used, the shrinkage of the resin composition after heat curing is large, and gaps with the through-hole walls are formed after curing, or voids are easily generated in the cured product of the hole filling portion, which is not preferable. Among these curing catalysts, dicyandiamide, melamine, acetoguanamine, benzoguanamine, 3,9-bis[2-(3,5-diamino-2,4,6-triazaphenyl)ethyl]-2 It is known that guanamine and its derivatives, such as ,4,8,10-tetraoxaspiro[5.5]undecane, and their organic acid salts and epoxy adducts have adhesion to copper and rust prevention properties, and epoxy resins It not only acts as a curing catalyst, but can contribute to the prevention of discoloration of copper of a printed wiring board.

A hardening accelerator can be used individually by 1 type or in mixture of 2 or more types.

In this invention, the compounding quantity of a hardening accelerator becomes like this with respect to 100 mass parts of epoxy resins containing (A) bisphenol E-type epoxy resin. Preferably it can use in 0.01-20 mass parts. Moreover, in the case of a metal catalyst, 10-550 ppm is preferable in conversion of a metal with respect to 100 mass parts of epoxy resins containing (A) bisphenol E-type epoxy resin, and 25-200 ppm is preferable.

[(C) Filler]

The composition of the present invention contains (C) a filler. By mix|blending a filler, hardening characteristics can be improved by making CTE close to conductor layers, such as copper, which exist around an insulating layer. As the filler, any conventionally known inorganic filler and organic filler can be used, and although it is not limited to a specific one, an inorganic filler capable of suppressing cure shrinkage of a coating film and contributing to improvement of properties such as adhesion and hardness is preferable. Examples of the inorganic filler include barium sulfate, barium titanate, amorphous silica, crystalline silica, fused silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, silicon nitride, aluminum nitride, boron nitride. , alumina, magnesium oxide, magnesium hydroxide, titanium oxide, mica, talc, Neuburg silicate, organic bentonite, non-metal fillers such as zirconium phosphate, copper, tin, zinc, nickel, silver, palladium, aluminum, iron, cobalt, gold , platinum, and metal fillers such as silicon, and may be used alone or in combination of two or more thereof.

In the present invention, among the above, it is preferable to use either or both of calcium carbonate and silica as the (C) filler. By mix|blending a calcium carbonate, it can be set as the dry film excellent in softness|polishing property, and CTE can be reduced more and TCT resistance can be improved by mix|blending a silica. Silica may be either amorphous or crystalline, or a mixture thereof. In particular, amorphous (fused) silica is preferable. The calcium carbonate may be either natural ground calcium carbonate or synthetic precipitated calcium carbonate. In particular, when the composition of the present invention is used for filling holes, it is preferable to use calcium carbonate excellent in abrasiveness as the (C) filler.

Examples of the shape of the filler include spherical, needle-like, plate-like, scale-like, hollow, irregular, hexagonal, cubic, flaky, and the like, but from the viewpoint of high filling of the inorganic filler, spherical shape is preferable. Moreover, it is preferable that it is 25 micrometers or less, and, as for the average particle diameter of a filler, it is more preferable that it is 5 micrometers or less. As a lower limit, it is 1 nm or more, for example. On the other hand, when the composition of the present invention is 25 µm or less, when the composition of the present invention is used as a hole filling material, the filling property with respect to the hole portion of the printed wiring board becomes good, and when the conductor layer is formed in the hole part, the smoothness becomes good. is effective. In addition, the average particle diameter can be calculated|required with the laser diffraction type particle diameter distribution measuring apparatus.

It is preferable that the compounding quantity of (C) filler in the composition of this invention is 1-90 mass % based on the composition whole quantity excluding a solvent, It is more preferable that it is 10-90 mass %, It is 30-80 mass % more preferably. If the compounding quantity of a filler is 1 mass % or more, thermal expansion can be suppressed, heat resistance can be improved, and grinding|polishing property and adhesiveness can be exhibited. On the other hand, when it is 90 mass % or less, the hardness of hardened|cured material improves, generation|occurrence|production of a crack can be suppressed, and liquid paste formation easily occurs, and printability, hole filling property, etc. are acquired.

Although it is essential that the composition of this invention contains the said (A), (B), and (C) component, depending on a use, it may contain other components further.

(other epoxy resins)

In the composition of this invention, although it is essential to contain (A) bisphenol E-type epoxy resin as an epoxy resin, it is a range which does not impair the desired effect of this invention, and contains another epoxy compound by 1 type or 2 types or more. You can do it.

The epoxy compound is a compound having an epoxy group, and any conventionally known one can be used. Examples of the epoxy compound include a bifunctional epoxy compound having two epoxy groups in a molecule, and a polyfunctional epoxy compound having a large number of epoxy groups in a molecule. Moreover, the hydrogenated bifunctional epoxy compound may be sufficient.

As an epoxy compound, For example, bisphenol A epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, brominated bisphenol A type epoxy resin, bisphenol S type epoxy resin, phenol novolak type epoxy resin, cresol novolac Epoxy resin, bisphenol A novolak epoxy resin, biphenyl type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, triphenylmethane type epoxy resin, alicyclic epoxy resin, aliphatic Chain epoxy resin, phosphorus-containing epoxy resin, anthracene-type epoxy resin, norbornene-type epoxy resin, adamantane-type epoxy resin, fluorene-type epoxy resin, aminophenol-type epoxy resin, aminocresol-type epoxy resin, alkylphenol-type epoxy resin, etc. this is used Any of a solid epoxy resin, a semi-solid epoxy resin, and a liquid epoxy resin may be sufficient as an epoxy compound.

Here, in this specification, a solid epoxy resin refers to an epoxy resin that is in a solid state at 40°C, a semi-solid epoxy resin refers to an epoxy resin that is solid at 20°C and liquid at 40°C, and a liquid epoxy resin is a liquid epoxy resin at 20°C. Epoxy resin.

The determination of the liquid can be performed in accordance with the Attachment 2 "Method for Confirming Liquid Level" of the Ordinance on Testing and Characteristics of Dangerous Substances (Ordinance of the Ministry of Autonomy of Japan, 1989 No. 1).

(1) device

constant temperature bath:

It is equipped with a stirrer, heater, thermometer, and automatic temperature controller (one that can control the temperature at ±0.1°C), and uses a depth of 150 mm or more.

In addition, in the determination of the epoxy resin used in the Examples to be described later, a combination of a low-temperature constant temperature water tank (model BU300) manufactured by Yamato Chemical Co., Ltd. and an input type thermostat (model BF500) was used, and approximately 22 liters of tap water was heated at a low temperature. Put it in a constant temperature water bath (model BU300), turn on the power supply of the thermomate (model BF500) attached to it, set it to the set temperature (20°C or 40°C), and set the water temperature to the set temperature ±0.1°C for the thermomate (model BF500). is fine-tuned, but any device that can adjust the same can be used.

examiner:

As a test tube, as shown in FIG. 2, it is made of flat-bottomed cylindrical transparent glass with an inner diameter of 30 mm and a height of 120 mm, and marked lines 31 and 32 are respectively provided at 55 mm and 85 mm heights from the bottom of the tube, and the inlet of the test tube is Sealed with a rubber stopper (33a), the test tube for liquidity determination (30a), the same size, similarly marked lines, and sealed the entrance of the test tube with a rubber stopper (33b) with a hole for inserting and supporting the thermometer in the center and use the test tube 30b for temperature measurement in which the thermometer 34 is inserted into the rubber stopper 33b. Hereinafter, the marked line 55 mm high from the bottom of the tube is called "Line A", and the marked line 85 mm high from the bottom of the tube is called "Line B".

As the thermometer 34, the one for measuring the freezing point prescribed in JIS B7410 (1982) "Glass thermometer for testing of petroleum products" (SOP-58 scale range of 20 to 50 ° C) is used, but the temperature range of 0 to 50 ° C can be measured. It's good if you can.

(2) Procedure of the test

A sample left at a temperature of 20±5° C. under atmospheric pressure for 24 hours or more was placed in the test tube 30a for liquid determination shown in FIG. 2(a) and the test tube 30b for temperature measurement shown in FIG. up to the line The two test tubes (30a, 30b) are placed upright in a low-temperature constant temperature water bath so that the B line is below the water surface and left still. The lower end of the thermometer should be 30 mm below the A line.

After the sample temperature reaches the set temperature ±0.1°C, keep it as it is for 10 minutes. After 10 minutes, the liquid test tube 30a is taken out from the low-temperature constant-temperature water bath, immediately laid down on a horizontal test bench, and the time the tip of the liquid level in the test tube moved from line A to line B is measured with a stopwatch, record A sample is judged to be a liquid phase when the measured time is less than 90 seconds at a set temperature, and a solid phase to exceed 90 seconds.

As a solid epoxy resin, DIC company HP-4700 (naphthalene type epoxy resin), DIC company EXA4700 (tetrafunctional naphthalene type epoxy resin), Nippon Kayaku Corporation NC-7000 (naphthalene skeleton containing polyfunctional solid epoxy resin), such as naphthalene types epoxy resin; an epoxidized product (trisphenol-type epoxy resin) of a condensate of a phenol and an aromatic aldehyde having a phenolic hydroxyl group, such as EPPN-502H (trisphenol epoxy resin) manufactured by Nippon Kayaku Corporation; Dicyclopentadiene aralkyl type epoxy resins, such as Epiclon HP-7200H (dicyclopentadiene skeleton containing polyfunctional solid epoxy resin) by DIC; Biphenyl aralkyl type epoxy resins, such as Nippon Kayaku Co., Ltd. NC-3000H (biphenyl skeleton containing polyfunctional solid epoxy resin); Biphenyl/phenol novolak-type epoxy resins, such as NC-3000L by Nippon Kayaku Co., Ltd.; Novolac-type epoxy resins, such as Epiclon N660 by DIC, Epiclon N690, and EOCN-104S by Nippon Kayaku; Biphenyl type epoxy resins, such as YX-4000 by Mitsubishi Chemical Corporation; Phosphorus containing epoxy resins, such as TX0712 by the Shin-Nittetsu Sumikin Chemical company; Tris(2,3-epoxypropyl)isocyanurate, such as TEPIC by Nissan Chemical Industry Co., Ltd., etc. are mentioned.

As a semi-solid epoxy resin, DIC Corporation Epiclone 860, Epiclone 900-IM, Epiclone EXA-4816, Epiclone EXA-4822, Asahi Chiba Corporation Araldite AER280, Toto Chemical Corporation Epottoto YD-134, Japan Bisphenol-A epoxy resins, such as jER834 and jER872 by an epoxy resin company, and ELA-134 by Sumitomo Chemical Co., Ltd.; Naphthalene-type epoxy resins, such as Epiclon HP-4032 by DIC; Phenol novolak-type epoxy resins, such as DIC Corporation Epiclon N-740, etc. are mentioned.

Examples of the liquid epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, phenol novolak type epoxy resin, tert-butyl-catechol type epoxy resin, glycidylamine type epoxy resin, aminophenol type epoxy resin An epoxy resin, an alicyclic epoxy resin, etc. are mentioned.

In the composition of this invention, you may use together a semi-solid epoxy resin and a solid epoxy resin with liquid (A) bisphenol E-type epoxy resin. In this case, it is preferable that the compounding quantity of (A) component is 1-45 mass % based on the composition whole quantity in conversion of solid content, It is more preferable that it is 1-30 mass %, It is still more preferable that it is 1-10 mass %.

A semi-solid or solid epoxy resin can be used individually by 1 type or in combination of 2 or more types. The blending amount of the semi-solid and solid epoxy resin is preferably 5 to 50 mass %, more preferably 10 to 40 mass %, more preferably 10 to 35 mass %, based on the total amount of the composition, in conversion of the solid content excluding the solvent. desirable.

Moreover, you may use other liquid components, such as a bisphenol A epoxy resin, together with (A) bisphenol E epoxy resin as a liquid epoxy resin in the range which can maintain heat resistance, flexibility, and water absorption. In this case, (A) the compounding amount of the bisphenol E-type epoxy resin is preferably 1-90 mass %, more preferably 1-70 mass %, furthermore, 1-50 mass %, based on the total amount of the liquid epoxy resin. desirable.

In addition, when using the composition of this invention as a liquid resin composition for hole filling, for example, it is preferable to use a polyfunctional epoxy resin together with (A) bisphenol E-type epoxy resin. (A) By using a polyfunctional epoxy resin together with a component, there exists an effect which can improve heat resistance further. In this case, the compounding quantity of component (A) is preferably 10 mass % or more, more preferably 15 to 80 mass %, and 15 to 60 mass % with respect to the total amount of the epoxy resin containing the bisphenol E-type epoxy resin. more preferably.

In addition, when using the composition of this invention as a liquid resin composition for hole filling, for example, you may melt|dissolve a solid epoxy resin in a solvent with (A) bisphenol E epoxy resin, and may use it. In this case, as the solvent, ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, petroleum solvents and the like can be used. Specifically, Ketones, such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; Cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether glycol ethers such as; esters such as ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol butyl ether acetate, methyl lactate, ethyl lactate, and butyl lactate; alcohols such as ethanol, propanol, ethylene glycol, and propylene glycol; aliphatic hydrocarbons such as octane and decane; Petroleum solvents, such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha, etc. are mentioned. These solvents may be used independently and may use 2 or more types together. In addition, what is necessary is just to determine the compounding quantity of a solvent suitably based on workability|operativity etc. in the range from which the desired effect of this invention is acquired.

(coloring agent)

If necessary, the composition of the present invention may contain a colorant. By containing a coloring agent, when especially the composition of this invention is used for formation of surface layers, such as a soldering resist layer, concealability, such as a circuit, can be improved. As a coloring agent, commonly known coloring agents, such as red, blue, green, yellow, white, and black, can be used, Any of a pigment, dye, and a pigment|dye may be sufficient. Specific examples include those to which a color index (C.I.; issued by The Society of Dyers and Colorists) number is assigned. However, it is preferable that it is a coloring agent which does not contain a halogen from a viewpoint of environmental load reduction and an influence on a human body.

Examples of the red colorant include monoazo, disazo, azolake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, and quinacridone. As the blue colorant, there are metal-substituted or unsubstituted phthalocyanine-based and anthraquinone-based compounds, and pigment-based compounds classified as pigments. As a green colorant, there exist a metal-substituted or unsubstituted phthalocyanine type, anthraquinone type, and a perylene type similarly. Examples of the yellow colorant include monoazo, disazo, condensed azo, benzimidazolone, isoindolinone, and anthraquinone. As a white colorant, titanium oxide, such as a rutile type and an anatase type, etc. are mentioned. Examples of the black colorant include titanium black, carbon black, graphite, iron oxide, anthraquinone, cobalt oxide, copper oxide, manganese, antimony oxide, nickel oxide, perylene and aniline pigments, sulfide. Molybdenum, bismuth sulfide, etc. are mentioned. In addition, you may add colorants, such as purple, orange, and brown, for the purpose of adjusting a color tone. A colorant can be used individually by 1 type or in combination of 2 or more type.

Although the compounding quantity of a coloring agent is not specifically limited, It is preferable that it is 0.1-10 mass % based on the composition whole quantity excluding a solvent, and it is more preferable that it is 0.1-7 mass %.

(thermoplastic resin (polymer resin))

The composition of this invention can further contain a thermoplastic resin in order to improve the mechanical strength of the cured film obtained. As the thermoplastic resin, the hydroxyl group of the hydroxyether moiety present in the backbone of the thermoplastic polyhydroxypolyether resin, the phenoxy resin which is a condensate of epichlorohydrin and various difunctional phenol compounds, or various acid anhydrides or acid chlorides is used. The esterified phenoxy resin, polyvinyl acetal resin, polyamide resin, polyamideimide resin, a block copolymer, etc. are mentioned. A thermoplastic resin can be used individually by 1 type or in combination of 2 or more type. What acylated the hydroxyl group of a phenoxy resin is preferable since it is excellent in an electrical property.

Polyvinyl acetal resin is obtained by acetalizing polyvinyl alcohol resin with an aldehyde, for example. The aldehyde is not particularly limited and includes, for example, formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, amylaldehyde, hexylaldehyde, heptylaldehyde, 2-ethylhexylaldehyde, cyclohexylaldehyde, furfural, benzaldehyde, 2- methylbenzaldehyde, 3-methylbenzaldehyde, 4-methylbenzaldehyde, p-hydroxybenzaldehyde, m-hydroxybenzaldehyde, phenylacetaldehyde, β-phenylpropionaldehyde, etc. are mentioned, and butyraldehyde is preferable.

Specific examples of the phenoxy resin include FX280 and FX293 manufactured by Toto Chemical Corporation, YX8100, YX6954, YL7213, and YL7218 manufactured by Mitsubishi Chemical. Moreover, as a specific example of polyvinyl acetal resin, Sekisui Chemical Co., Ltd. S-Rec KS series, Hitachi Kasei Kogyo Co., Ltd. KS5000 series, Nippon Kayaku Co., Ltd. BP series as polyamide resin, Hitachi Kasei Kogyo Co., Ltd. KS9000 series as polyamideimide resin. and the like.

When the thermoplastic polyhydroxypolyether resin has a fluorene skeleton, it has a high glass transition point and is excellent in heat resistance. Thus, the obtained cured film has a low coefficient of thermal expansion and a high glass transition point in a well-balanced manner. In addition, since the thermoplastic polyhydroxypolyether resin has a hydroxyl group, it exhibits good adhesion to substrates and conductors, and the resulting cured film is difficult to be immersed with a roughening agent. Since it is easy to osmose|permeate into the interface of , the filler on the surface of a hardened-film becomes easy to fall out by a roughening process, and it becomes easy to form a favorable roughening surface.

As the thermoplastic resin, a block copolymer may be used. The block copolymer is a copolymer of a molecular structure in which two or more types of polymers having different properties are linked by a covalent bond to form a long chain.

As the block copolymer, A-B-A type or A-B-A' type block copolymer is preferable. Among the A-B-A-type and A-B-A'-type block copolymers, B in the center is a soft block, and the glass transition temperature (Tg) is low, preferably less than 0°C, and both outer A or A' are hard blocks and glass transition It is preferable that the temperature (Tg) is high, and it is comprised by the polymer unit, Preferably it is 0 degreeC or more. The glass transition temperature (Tg) is measured by differential scanning calorimetry (DSC). In addition, among A-B-A type and A-B-A' type block copolymers, A or A' contains a polymer unit having a Tg of 50°C or higher, and B is a block containing a polymer unit having a glass transition temperature (Tg) of -20°C or lower A copolymer is more preferred. In addition, among A-B-A type and A-B-A' type block copolymers, A or A' preferably has high compatibility with the bisphenol E type epoxy resin, and B has low compatibility with the above bisphenol E type epoxy resin it is preferable As described above, it is thought that a specific structure in the matrix is easily exhibited by using a block copolymer in which the blocks at both ends are compatible with the matrix and the central block is incompatible with the matrix.

Among the thermoplastic resins, a phenoxy resin, a polyvinyl acetal resin, a thermoplastic polyhydroxy polyether resin having a fluorene skeleton, and a block copolymer are preferable, and a phenoxy resin is particularly preferable.

1-20 mass parts is preferable with respect to 100 mass parts of epoxy resins, and, as for the compounding quantity of a thermoplastic resin, 1-10 mass parts is more preferable. When the compounding quantity of a thermoplastic resin is in the said range, a uniform roughened surface state is obtained easily.

(maleimide compound)

The composition of the present invention may further contain a maleimide compound. By mix|blending a maleimide compound, Tg can be improved more.

The maleimide compound is a compound having a maleimide skeleton, and any conventionally known compound can be used. The maleimide compound preferably has two or more maleimide skeletons, N,N'-1,3-phenylenedimaleimide, N,N'-1,4-phenylenedimaleimide, N,N'-4, 4-diphenylmethanebismaleimide, 1,2-bis(maleimide)ethane, 1,6-bismaleimidehexane, 1,6-bismaleimide-(2,2,4-trimethyl)hexane, 2, 2'-bis-[4-(4-maleimidephenoxy)phenyl]propane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethanebismaleimide, 4-methyl -1,3-phenylenebismaleimide, bis(3-ethyl-5-methyl-4-maleimidephenyl)methane, bisphenol A diphenyletherbismaleimide, polyphenylmethanemaleimide and oligomers thereof, and maleic It is more preferable that it is at least any 1 sort(s) of the diamine condensate which has mid frame|skeleton. The said oligomer is an oligomer obtained by condensing the maleimide compound which is a monomer among the above-mentioned maleimide compounds. A maleimide compound can be used individually by 1 type or in combination of 2 or more type.

Among the maleimide compounds, at least any one of a condensate of phenylmethane maleimide and a bismaleimide oligomer is more preferable. It is preferable that the said bismaleimide oligomer is an oligomer obtained by condensation of phenylmethanebismaleimide and 4, 4- diaminodiphenylmethane. As a commercial item of the condensate of phenylmethane maleimide, Yamato Chemical Co., Ltd. BMI-2300 etc. are mentioned. Moreover, as a commercial item of a bismaleimide oligomer, Yamato Chemical Co., Ltd. DAIMAID-100H etc. are mentioned.

Moreover, it is preferable that a maleimide compound is a maleimide compound represented by the following general formula (I).

In the general formula (I), R ¹ to R ³ each independently represent a hydrogen atom, a halogen atom or an organic group, and n represents an integer of 0 to 1. In the general formula (I), R ¹ to R ³ are preferably a hydrogen atom.

It is preferable that the said maleimide compound is a mixture of the maleimide compound represented by the said General formula (I). Moreover, it is more preferable that the average value of n in the said General formula (I) of a mixture is 0.1-1 at the point from which solubility of a mixture becomes high and CTE of the hardened|cured material of a resin layer becomes lower. The larger the average value of n, the higher the solubility of the mixture. In the case of a mixture of maleimide compounds having an average value of n of 0.1 to 1, even if the resin layer of the dry film is thermally cured at a low temperature, a cured product having a high Tg can be formed, and it is also possible to use a thin substrate with low heat resistance.

It is preferable that it is 2-50 mass % based on the composition whole quantity except a solvent and a filler, and, as for the compounding quantity of a maleimide compound, it is more preferable that it is 10-50 mass %. When it is 2 mass % or more, CTE of hardened|cured material becomes low and Tg of hardened|cured material becomes higher. Moreover, when it is 50 mass % or less, breaking strength becomes high.

(Other ingredients)

When the composition of the present invention is used as a dry film for an interlayer insulating material and a solder resist, for example, if necessary, conventionally known thickeners such as asbesto, orben, bentone, finely divided silica, silicone-based, fluorine-based, polymer Antifoaming agents and/or leveling agents, such as antifoaming agents, adhesion-imparting agents such as thiazole-based, triazole-based and silane coupling agents, flame retardants, titanate-based, and aluminum-based conventionally known additives can be used.

(solvent)

When the composition of the present invention is used, for example, as a dry film for an interlayer insulating material and a solder resist, a solvent for preparation of the composition, adjustment of viscosity for application to a substrate or carrier film, formation of a resin layer of a dry film, etc. can be used It does not specifically limit as a kind of solvent, A conventionally well-known solvent can be used. In addition, the compounding quantity of a solvent is not limited, either.

In particular, when forming a dry film using the composition of the present invention, as a solvent, it is preferable to use two solvents having a boiling point of 100° C. or more and a difference in boiling point of 5° C. or more, thereby providing excellent flexibility. It becomes possible to obtain a dry film. The difference in boiling points becomes like this. Preferably it is 10 degreeC or more, More preferably, it is 20 degreeC or more. In addition, in this specification, when the boiling point of a solvent has a width|variety, let the initial distillation point - the end point of distillation be a boiling point.

Examples of the solvent having a boiling point of less than 100°C include diethyl ether, carbon disulfide, acetone, chloroform, methanol, n-hexane, ethyl acetate, 1,1,1-trichloroethane, carbon tetrachloride, methyl ethyl ketone, isopropyl alcohol, trichloro Ethylene, isopropyl acetate, etc. are mentioned.

Examples of the solvent having a boiling point of 100°C or higher include methoxypropanol such as isobutyl alcohol, toluene, methyl isobutyl ketone, n-butanol, butyl acetate and 2-methoxypropanol, isobutyl acetate, tetrachloroethylene, and ethylene glycol monomethyl ether. , methyl butyl ketone, isopentyl alcohol, ethylene glycol monoethyl ether, N,N-dimethylformamide (DMF), ethylene glycol monoethyl ether acetate, turpentine, cyclohexanone, and ethylene glycol monobutyl ether. .

Moreover, as a solvent with a boiling point of 100 degreeC or more, Xylene, petroleum naphtha, Maruzen Sekiyu Chemical Co., Ltd. Swasol 1000 (C8-10: high boiling point aromatic hydrocarbon), Swasol 1500 (high boiling point aromatic hydrocarbon), Standard Seki Solvesso 100 made by Osaka Hatsubaisho Corporation (9 to 10 carbon atoms: high boiling point aromatic hydrocarbon), Solvesso 150 (C10 to 11: high boiling point aromatic hydrocarbon), Sankyo Chemical Company solvent #100, solvent #150, Shell Chemical and Shellsol A100 and Shellsol A150 manufactured by Japan Corporation, Idemitsu Kosan Co., Ltd. Ipsol No. 100 (the main component is an aromatic hydrocarbon having 9 carbon atoms), and Ipsol No. 150 (the main component is an aromatic hydrocarbon having 10 carbon atoms), and the like. The high boiling point aromatic hydrocarbon preferably contains 99% by volume or more of the aromatic component. Further, the high boiling point aromatic hydrocarbon preferably contains less than 0.01% by volume of each of benzene, toluene and xylene.

When a dry film is formed using the composition of the present invention, three or more solvents having boiling points of 100°C or higher may be blended with the composition, and in this case, any two solvents having different boiling points among three or more solvents may be used. Moreover, the solvent whose boiling point is 100-230 degreeC among the solvents of 100 degreeC or more is preferable, and the solvent whose boiling point is 100-220 degreeC is more preferable. It is difficult for a solvent to remain|survive in the resin layer of a dry film after thermosetting or an annealing process that a boiling point is 230 degrees C or less. The solvent is more preferably toluene, N,N-dimethylformamide, methoxypropanol, methyl isobutyl ketone, cyclohexanone, petroleum naphtha, or an aromatic hydrocarbon having 8 or more carbon atoms. Especially, the combination of toluene and cyclohexane, the combination of toluene and methyl isobutyl ketone, and the combination of cyclohexanone and methyl isobutyl ketone are more preferable.

It is preferable that it is 10-150 mass parts with respect to 100 mass parts of resin layers of the dry film except a solvent, and, as for the compounding quantity of the solvent before drying, it is more preferable that it is 25-100 mass parts. When the compounding quantity of a solvent is 10 mass parts or more, solubility improves and adjustment of the quantity of a residual solvent becomes easy, on the other hand, when it is 150 mass parts or less, control of the thickness of a resin layer becomes easy.

Moreover, the composition of this invention can also be applied to formation of hardened films of printed wiring boards, such as an interlayer insulating material, a coverlay, or a soldering resist, as a liquid resin composition.

(Other ingredients)

When using the composition of the present invention, for example, as a liquid resin composition for filling holes, and if necessary, in order to provide storage stability during storage, boric acid ester compound, hydroquinone, hydroquinone monomethyl ether, tert - Well-known and usual thermal polymerization inhibitors such as butylcatechol, pyrogallol, and phenothiazine; Well-known and usual thickeners or thixotropic agents such as clay, kaolin, organic bentonite, and montmorillonite; / Or, well-known and usual additives, such as adhesion-imparting agents, such as a leveling agent, an imidazole type, a thiazole type, a triazole type, and a silane coupling agent, can be added. In particular, when organic bentonite is used, the portion protruding from the surface of the hole tends to be formed in a protruding state that is easy to be polished and removed, and it is preferable because it is excellent in polishing properties.

The thermosetting resin composition of the present invention can obtain excellent properties of a cured product by heating. Therefore, the thermosetting resin composition of the present invention does not need to contain a component that itself is polymerized by light irradiation, such as a photopolymerizable monomer.

[Form of composition]

The form of the composition of this invention may be provided as a liquid resin composition whose viscosity was adjusted suitably, and as mentioned above, it is good also as a dry film which apply|coated the composition on the support base film, and dried the solvent. Moreover, it is good also as a prepreg sheet in which the composition of this invention was made to coat and/or impregnate to sheet-like fibrous base materials, such as glass cloth, glass and an aramid nonwoven fabric, and made it semi-hardened. Examples of the supporting base film include polyolefins such as polyethylene and polyvinyl chloride, polyesters such as polyethylene terephthalate, polycarbonates, polyimides, and metal foils such as release paper, copper foil, and aluminum foil. In addition, you may give a mold release process other than a mad process and corona treatment to a support base film.

The liquid resin composition, dry film, or prepreg using the composition of the present invention is directly coated on an inner circuit board on which a circuit is formed, dried and cured, or integrally formed by heating and laminating the dry film, and then, in an oven You may harden by medium or hot plate press. In the case of a prepreg, it is also possible to use a method of overlapping the inner circuit board, sandwiching the metal plate with a release film interposed therebetween, pressurizing and heating, and pressing.

Among the above steps, the method of laminating or hot plate pressing is preferable because fine irregularities caused by the inner layer circuit are resolved when heated and melted and cured as they are, so that a multilayer plate with a flat surface is finally obtained. Moreover, when laminating or hot-plate pressing the base material with an inner-layer circuit and the film or prepreg of the composition of this invention, copper foil or the base material with a circuit may be laminated|stacked simultaneously.

A hole is punched in the substrate obtained in this way with a semiconductor laser such as a CO ₂ laser or UV-YAG laser, or a drill. The hole may be a through hole (through hole) for the purpose of conducting the front and back of the substrate, or a partial hole (conformal via) for the purpose of conducting an inner layer circuit and a circuit on the surface of the interlayer insulating layer. do.

After drilling, in order to remove the residue (smear) existing on the inner wall or bottom of the hole and to express the anchor effect with the conductor layer (the metal plating layer to be formed thereafter), a roughened surface of fine concavo-convex shape is formed on the surface It carries out simultaneously with the roughening liquid containing oxidizing agents, such as a commercially available desmear liquid (roughening agent) or permanganate, dichromate, ozone, hydrogen peroxide/sulfuric acid, and nitric acid for the purpose of doing this.

Next, after forming the film surface which produced the hole from which the residue was removed with the desmear liquid, and the fine grooving|roughness-like roughening surface, a circuit is formed by a subtractive method, a semi-additive method, etc. In either method, after electroless plating, electrolytic plating, or both plating, heat treatment called annealing is performed at about 80 to 200 ° C for 10 to 60 minutes for the purpose of stress relief and strength improvement of the metal. also be

There is no restriction|limiting in particular as metal plating used here, such as copper, tin, solder, nickel, A plurality of metal platings may be used in combination. In addition, it is also possible to substitute metal sputtering or the like in place of the plating used here.

The composition of this invention can be used suitably for manufacture of a printed wiring board, and can be used especially suitably for formation of insulating layers of a printed wiring board, such as an interlayer insulating layer and a soldering resist, and the use of hole filling, such as a through hole and a via hole.

[Dry Film]

The dry film of this invention can be manufactured by apply|coating the composition of this invention on a carrier film, drying, and forming the resin layer as a dry coating film. On the resin layer, if necessary, a protective film can be laminated.

As a material of a carrier film, polyethylene terephthalate (PET) etc. can be used suitably. The thickness of the carrier film is suitably from 8 to 75 mu m. In addition, as a material of a protective film, the thing similar to what is used for a carrier film can be used, PET or polypropylene (PP) is preferable. The thickness of a protective film is 5-50 micrometers suitably. Moreover, in this invention, a resin layer is formed by apply|coating and drying the composition of this invention on the said protective film, and you may laminate|stack a carrier film on the surface. That is, when manufacturing a dry film in this invention, you may use any of a carrier film and a protective film as a film which apply|coats the composition of this invention.

Here, as a coating method of a composition, methods, such as a dip coating method, the flow coating method, the roll coating method, the bar coater method, the screen printing method, the curtain coating method, can be used. Moreover, as a volatilization drying method, the thing equipped with the heat source of the air heating system by steam, such as a hot-air circulation type drying furnace, an IR (infrared) furnace, a hot plate, a convection oven, can be used.

In the dry film of the present invention, the amount of residual solvent in the resin layer formed as described above is preferably less than 1% by mass, more preferably 0.01 to 0.8% by mass, based on the total amount of the resin layer containing the solvent. By setting the amount of residual solvent in the resin layer within the above range, while suppressing cracks and powder fall of the dry film, the peelability is improved, the residual bubble is reduced, and the occurrence of cracks can be more effectively suppressed. .

[Composition for filling holes]

In the case of using the composition of the present invention as a liquid resin composition for filling holes, the via hole of the printed wiring board or the It can easily fill in hole parts, such as a through hole. Subsequently, for example, the composition is cured by heating at about 90 to 180° C. for about 30 to 90 minutes. Then, among the hardened|cured composition, the unnecessary part protruding from the board|substrate surface can be easily removed by physical polishing, and it can be set as a flat surface. In addition, physical polishing can be performed by the conventionally performed and well-known method.

[Cured material and printed wiring board]

The hardened|cured material of this invention is obtained by hardening|curing the resin layer of the composition or dry film of this invention, The printed wiring board of this invention is equipped with such hardened|cured material of this invention. Although the manufacturing method is demonstrated below, it is not limited to this.

[Manufacture of printed wiring board]

Manufacture of the printed wiring board using the composition of this invention can be performed, as shown, for example to FIGS. 3-5. In the example shown in FIG. 3, first, a through hole is drilled in the substrate 1 on which the copper foil 2 is laminated, and the through hole 3 is formed by electroless plating on the wall surface and the surface of the copper foil ( 3 (a)), a plating film 4a is formed on the surface of the substrate 1 and the inner wall of the through hole 3 (Fig. 3 (b)). Next, the liquid resin composition 5 using the composition of the present invention is filled in the through-hole 3 (FIG. 3(c)), and after curing by heat, the unnecessary portion protruding from the through-hole 3 is polished and flattened (FIG. 3(d)). Next, after forming the plating film 4b on the surface of the substrate 1 (FIG. 3(e)), an etching resist 6 is formed (FIG. 3(f)), and the non-resist portion is etched Then, the etching resist 6 is peeled off to form the conductor circuit layer 7a (FIG. 3(g)).

Next, on the conductor circuit layer 7a, an interlayer insulating layer 8a is formed with the dry film using the composition of this invention, and the opening 9a is formed (FIG.4(a)). Next, a plating film 4c is formed on the entire surface (Fig. 4(b)), a plating resist layer 10 is formed on the plating film 4c, and then electrolytic plating is further performed to thicken the conductor circuit portion. Thus, an electrolytic plating film 4d is formed (FIG. 4(c)). Next, after the plating resist layer 10 is peeled off, the electroless plating film 4c below it is dissolved and removed by etching to form an independent conductor circuit (including the via hole 11a) (shown in Fig. 4). (d)).

In another example shown in Fig. 5, after the core substrate manufacturing process shown in Fig. 3(d) is completed, the conductor layers on both surfaces of the core substrate 1 are etched, and the substrate 1 is formed on both surfaces. While the one conductor circuit layer 7b is formed, a land 12 is formed in a part of the conductor circuit layer 7b connected to the through hole 3 (FIG. 5(a)). Next, an interlayer insulating layer 8b is formed on the upper and lower surfaces of the substrate 1 (FIG. 5(b)), and a via hole 11b is formed in the interlayer insulating layer 8b located directly above the land 12. formed (FIG. 5(c)). Next, a plating layer is formed in the via hole 11b and on the interlayer insulating layer 8b, and an etching resist is formed thereon, followed by etching, and a second conductor circuit layer 7c is formed on the interlayer insulating layer 8b. to form (FIG. 5 (c)). Each of the first and second conductor circuit layers 7b and 7c conducts through the via hole 11b, and the conductor circuit layers 7b on both sides of the substrate conducts through the through hole 3, respectively. Next, on each interlayer insulating layer 8b and the second conductor circuit layer 7c, a soldering resist layer 13 is formed using the composition of the present invention, and solder bumps 14 are formed on the upper soldering resist layer 13. ) is formed (FIG. 5(c)). Further, by plating the surface of the conductor circuit layer 7c exposed from the lower opening 9b, a multilayer wiring board as a connection terminal can be obtained.

Example

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples of the present invention, but it goes without saying that the present invention is not limited to the following Examples. In addition, in the following, "part" and "%" are both based on mass unless otherwise indicated.

<Production of thermosetting resin composition>

Each component is blended and stirred according to the formulation shown in Tables 1 to 5 below, kneaded and dispersed with a three roll mill, and the compositions for liquid resin compositions of Examples 1 to 8 and Comparative Examples 1 to 7 have a viscosity of 250 to 600 dPa. - s (rotational viscometer 5 rpm, 25 degreeC), about the composition for dry films of Examples 9-22 and Comparative Examples 8-12, it adjusted so that it might become a viscosity 0.5-20 dPa*s.

<Production of dry film>

Using a bar coater, the compositions of Examples 9 to 22 and Comparative Examples 8 to 12 obtained above were subjected to a carrier film (PET film; Toray) so that the film thickness after drying became the film thickness shown in Tables 6 to 8 and 10 below. Co., Ltd. Lumirer 38R75, thickness 38 micrometers) was apply|coated. Then, it dries for 5 to 10 minutes at 70-120 degreeC (average 100 degreeC) in a hot-air circulation type drying furnace so that residual content of the organic solvent after drying may become the quantity shown in following Tables 6-8, 10, and a carrier film The dry coating film which has a resin layer on it was obtained. Then, with a roll laminator, the protective film was stuck on the resin layer at the temperature of 70 degreeC, and the dry film of the Example and the comparative example which sandwiched both surfaces with the film was obtained.

<Measurement of residual content (%) of organic solvent in dry film>

After peeling a carrier film and a protective film from the dry film of each Example and a comparative example, about 1.2 g of resin layers were extract|collected, put into the container with a stopper, and the mass (W) of the collect|collected resin layer was precisely weighed. To this container, one drop of ethyl 3-ethoxypropionate as an internal standard was added with a pipette, and the mass (We) was accurately weighed. Then, 5 ml of acetone was added with a hole pipette, the stopper was closed, the container was sufficiently shaken, and the collected resin layer was dissolved. Then, this solution was filtered with a filter having an eye size of 0.5 µm, the composition of the filtrate was analyzed by gas chromatography (TRACEGCULTRA manufactured by Thermo Fisher Scientific), and from a calibration curve prepared separately, the organic solvent per 1 g of the internal standard substance The mass (Ws) of From these, the residual content of the organic solvent was calculated according to the following formula.

Residual content of organic solvent (mass %) = (We × Ws/W) × 100

In addition, the measurement conditions in gas chromatography are as follows. Column: Capillary column DB-1MS (30 m×0.25 mm) manufactured by Agilent Technologies, Detector: MS (ITQ900), Carrier gas: Helium, Injector temperature: 300° C., Detector temperature: 230° C., Column temperature conditions: Initial temperature 50 ℃, hold for 2 minutes at 50℃ after sample injection, increase the temperature to 300℃ at 10℃/min, and hold for 10 minutes after reaching 300℃.

<Flexibility of dry film (bending test)>

In accordance with JIS K5600-5-1 (ISO1519), using a cylindrical mandrel bending tester manufactured by BYK-Gardner, from the minimum diameter of the mandrel at which cracking of the dry film and peeling from the carrier film of each Example and Comparative Example begins to occur , the flexibility of the dry film was evaluated. The evaluation criteria are as follows. When the flexibility of the dry film is good, the flexibility of the resin layer is high, and cracks and powder fall can be suppressed.

(double-circle): There was no generation|occurrence|production of the crack of a resin layer, powder fall, and peeling of a carrier film in the diameter of (phi) 2 mm or less.

(circle): In the range of more than phi 2 mm and less than 5 mm, there was no generation|occurrence|production of the crack of a resin layer, powder fall, and peeling of a carrier film.

(triangle|delta): The crack of a resin layer, powder fall, and peeling of a carrier film generate|occur|produced in the range of more than (phi) 2 mm and less than 5 mm.

x: In the diameter of phi 5 mm or more, the crack of a resin layer, powder fall, and peeling of a carrier film generate|occur|produced.

<Glass transition temperature (Tg) and coefficient of thermal expansion (CTE(α1))>

(Preparation of evaluation sample of liquid composition)

The liquid resin composition of each Example and Comparative Example was applied with an applicator on the glossy side (copper foil) of GTS-MP foil (manufactured by Furukawa Circuit Foil Co., Ltd.), and cured at 150 ° C. for 60 minutes in a hot air circulation drying furnace.

(Preparation of evaluation sample of dry film)

For the dry film of each Example and Comparative Example, the protective film was peeled off, and on the glossy side (copper foil) of GTS-MP foil (manufactured by Furukawa Circuit Foil Co., Ltd.), batch-type vacuum pressurization laminator MVLP-500 (manufactured by Makey Co., Ltd.) ) was used for lamination. Lamination conditions were heat lamination under the conditions of 5 kgf/cm 2 , 80° C. for 1 minute and 1 Torr, and then leveling was performed under the conditions of 10 kgf/cm 2 , 80° C. for 1 minute with a hot plate press machine. Then, the resin layer was hardened at 180 degreeC for 60 minute(s) in the hot-air circulation type drying furnace. Moreover, regarding the composition containing the maleimide compound described in Examples 16 and 20, the resin layer was hardened at 220 degreeC for 60 minute(s).

(Measurement of glass transition temperature (Tg) and coefficient of thermal expansion (CTE(α1)))

Then, after peeling the hardened|cured material produced by the said method from copper foil, the sample was cut out to the measurement size (size of 3 mm x 10 mm), and it used for Seiko Instruments TMA6100. For TMA measurement, the temperature of the test weight of 5 g and the sample was raised from room temperature at a temperature increase rate of 10° C./min, and the measurement was performed twice in succession. The point of intersection of two tangents having different coefficients of thermal expansion in the second time was defined as the glass transition temperature (Tg), and evaluated as the coefficient of thermal expansion (CTE(α1)) in the region less than Tg. It can be said that heat resistance is high, so that Tg is high.

[Evaluation criteria for glass transition temperature (Tg)]

(double-circle): Tg is 190 degreeC or more.

(double-circle): Tg is 160 degreeC or more and less than 190 degreeC.

(circle): Tg 150 degreeC or more and less than 160 degreeC.

x: Tg is less than 150 degreeC.

[Evaluation criteria for coefficient of thermal expansion (CTE(α1))]

(double-circle): Less than 20 ppm.

○: 20 ppm or more to less than 35 ppm.

<Filling through Holo>

(Preparation of evaluation sample of liquid composition)

The liquid resin compositions of Examples and Comparative Examples were printed on a glass epoxy substrate having a thickness of 1.6 mm/through-hole diameter of 0.25 mm/pitch of 1 mm having through-holes in which a conductor layer was formed by panel plating, by screen printing, as follows. It was filled in the through hole under the condition. After charging, it was put in a hot air circulation drying furnace, and hardening was performed at 150 degreeC for 60 minutes, and the evaluation board|substrate was obtained. Fillability was evaluated by the filling degree of the hardened|cured material filled in the through-hole of this evaluation board|substrate.

<Print conditions>

Squeegee: Squeegee thickness 20mm, hardness 70°, bevel grinding: 23°,

Plate: PET100 mesh bias plate,

Pressure: 50kg, squeegee speed 30mm/Sec,

Squeegee angle: 80°.

(Preparation of evaluation sample of dry film)

The dry film of each Example and Comparative Example was peeled off the protective film, and a batch vacuum pressurized laminator MVLP-500 (manufactured by Meiki Corporation) was used, and on the same glass epoxy substrate as in "Preparation of evaluation sample of liquid composition" above, A dry film was laminated from both sides of the substrate by the same method as described in the above <Glass transition temperature (Tg) and coefficient of thermal expansion (CTE(α1))>, and the resin composition was filled in the through hole. Then, the resin layer was hardened by the hot-air circulation type drying furnace.

(Evaluation of filling properties)

Thereafter, the cross section passing through the center of the through hole in the substrate was cut and polished with a precision cutter, and the state of the cross section was observed with an optical microscope. The evaluation criteria evaluated according to the following. The number of observation through-holes was set to 200 holes.

(double-circle): The inside of all through-holes is completely filled with resin.

(circle): 1 or 2 holes generate|occur|produced through hole which is not completely filled with resin.

(triangle|delta): 3-50 holes generate|occur|produced through hole which is not completely filled with resin.

x: 51 holes or more generate|occur|produced the through hole which is not completely filled with resin.

<Occurrence of voids>

Generation|occurrence|production of the void in a through-hole was confirmed using the sample evaluated in the said <filling property into a through-hole>. The evaluation criteria evaluated according to the following. The number of observation through-holes was set to 200 holes.

(double-circle): No generation|occurrence|production of a void.

(circle): A void generate|occur|produces 1-2 holes.

(triangle|delta): 3-50 hole generation|occurrence|production of a void.

x: 51 or more holes generate|occur|produced a void.

<Measurement of absorption rate>

(Preparation of evaluation sample of liquid composition)

The liquid resin compositions of Examples and Comparative Examples were coated and cured in the same manner as described in <Glass Transition Temperature (Tg) and Coefficient of Thermal Expansion (CTE(α1))> above.

(Preparation of evaluation sample of dry film)

About the dry film of each Example and comparative example, the resin layer was hardened by the method similar to the method described in the said <glass transition temperature (Tg) and thermal expansion coefficient (CTE(α1))>.

(Measurement of absorption rate)

Then, after peeling the hardened|cured material from copper foil, after cutting out a sample to the measurement size (size of 50 mm x 50 mm), it dried at 100 degreeC for 2 hours, moisture was completely removed, and the mass ( W1) was measured. Then, the sample was immersed in distilled water managed at 23 degreeC +/-2 degreeC, and the measurement of the mass (W2) after 24 hours was performed. Water absorption was calculated|required by (W2-W1)/W1x100 (%).

◎◎: less than 0.3%.

(double-circle): 0.3% or more and less than 0.7%.

○: 0.7% or more and less than 1.0%.

(triangle|delta): 1.0 % or more and less than 1.4 %.

x: 1.4% or more.

<Cooling/heating cycle (crack suppression)>

(Preparation of evaluation sample of liquid composition)

The liquid resin compositions of Examples and Comparative Examples were filled into the through-holes in the same manner as in the method described in the above <Filling into through-holes>. Then, in a hot-air circulation drying furnace, it heated at 150 degreeC for 60 minutes, the resin layer was hardened, and the part of the resin protruding from the board|substrate surface was removed by buffing. Subsequently, a commercially available wet permanganate desmear (manufactured by ATOTECH), electroless copper plating (Thru Cup PEA, manufactured by Uemura Kogyo Co., Ltd.), and electrolytic copper plating treatment were performed in this order to obtain an evaluation substrate having cover plating specifications.

(Preparation of evaluation sample of dry film)

For the dry films of each Example and Comparative Example, using a batch vacuum pressurized laminator MVLP-500 (manufactured by Meiki Corporation), the dry film was removed from both sides of the substrate in the same manner as in the method described in the <Filling through holes>. After lamination, the resin composition was filled in the through hole. Then, the carrier film was peeled, and it heated at 180 degreeC for 30 minute(s) in a hot-air circulation type drying furnace, and hardened the resin layer. In addition, regarding the composition containing the maleimide compound described in Examples 16 and 20, the resin layer was hardened at 220 degreeC for 60 minute(s). Thereafter, via formation was performed using a CO ₂ laser processing machine (manufactured by Hitachi Via Mechanics) so as to have a top diameter of 65 µm and a bottom diameter of 50 µm.

Subsequently, a commercially available wet permanganate desmear (manufactured by ATOTECH), electroless copper plating (Thru Cup PEA, manufactured by Uemura Kogyo Co., Ltd.), and electrolytic copper plating treatment are performed in this order, and a copper thickness of 25 µm on a resin layer, via portion A copper plating treatment was performed to fill the Then, it hardened|cured at 190 degreeC for 60 minute(s) in a hot-air circulation type drying furnace, and the test board|substrate which gave the copper plating process which made it hardening was obtained.

(Implementation of cold-heat cycle)

For the test substrates of Examples and Comparative Examples obtained by the above method, one cycle of 30 minutes at -65 DEG C and 30 minutes at 150 DEG C was set, and 2000 and 2500 cycles of heat history were applied.

(Confirmation of cracks in through-holes)

The cross-sectional state of the center of the through hole was observed with an optical microscope in the same manner as described in the above <Fillability into the through hole>. The evaluation criteria evaluated according to the following. The number of observation through-holes was set to 200 holes.

(double-circle): No crack generation in both 2000 cycles and 2500 cycles.

(circle): No crack generation|occurrence|production in 2000 cycles. 1 to 5 cracks occurred at 2500 cycles.

x: A crack generate|occur|produced in 2000 cycles.

(Confirmation of cracks in vias)

In order to observe the state of the via bottom and wall surface with an optical microscope, the via center part was cut and grind|polished with the precision cutter, and the cross-sectional state was observed. The evaluation criteria evaluated according to the following. The number of observation vias was set to 100 holes.

(double-circle): No crack generation in both 2000 cycles and 2500 cycles.

(circle): No crack generation|occurrence|production in 2000 cycles. 1 to 5 cracks occurred at 2500 cycles.

x: A crack generate|occur|produced in 2000 cycles.

<Abrasiveness>

(Preparation of evaluation sample of liquid composition)

The liquid resin compositions of Examples and Comparative Examples were filled into the through-holes in the same manner as described in the above <Fillability into the through-holes>. After charging, it was put into a hot-air circulation drying furnace, and hardening was performed at 150 degreeC for 60 minutes, and the evaluation board|substrate was obtained.

(Preparation of evaluation sample of dry film)

For the dry films of each Example and Comparative Example, using a batch vacuum pressurized laminator MVLP-500 (manufactured by Makey Corporation), the dry film was applied only from one side of the substrate in the same manner as described in the <Filling through hole> method. After lamination, the resin layer was cured.

(Evaluation of abrasiveness)

The portion of the resin protruding from the substrate surface of the test substrates of each Example and Comparative Example obtained by the above method was subjected to physical polishing by buffing, and the number of passes until the resin was removed from the discharge portion was compared.

(double-circle): Polishing is possible in 2 passes or less.

○: Grinding is possible in 2-3 passes.

×: 4 passes or more.

<Evaluation of storage stability>

(Evaluation of storage stability of liquid composition)

For the liquid resin compositions of Examples 1 to 8 and Comparative Examples 1 to 7, the viscosity was measured at the initial stage and after storage at 25°C for 7 days, and the thickening rate was calculated by the following formula.

Thickening rate (%) = (viscosity after storage at 25°C for 7 days - initial viscosity)/initial viscosity × 100

◎: less than 10%

○: 10% or more and less than 30%

△: 30% or more and less than 50%

×: 50% or more

(Evaluation of storage stability of dry film)

About the dry film of each Examples 9-22 and Comparative Examples 8-12, the melt viscosity after initial stage and 25 degreeC 3 days storage was measured using "Reostress RS6000" manufactured by Thermo Fisher Scientific Co., Ltd. After peeling the carrier film and the protective film from the dry film of each Example and Comparative Example prepared in the size of 30 mm × 30 mm, it is loaded on a parallel plate having a diameter of 20 mm, and the starting temperature is from 40 ° C to 150 ° C, The melt viscosity was measured under the conditions of a temperature rise temperature of 3°C/min, a vibration of 1 Hz, and a strain of 2deg to determine the minimum melt viscosity, and the thickening rate was obtained by the following formula.

Thickness rate (%) = (minimum melt viscosity after storage at 25°C for 3 days - initial minimum melt viscosity) / initial minimum melt viscosity x 100

◎: less than 30%

○: 30% or more and less than 50%

*1) EPOX-MK R710: made by PRINTEC (Bisphenol E-type epoxy resin, epoxy equivalent 160 to 180 g/eq, liquid)

*2) JER828: manufactured by Mitsubishi Chemical Co., Ltd. (bisphenol A type epoxy resin, epoxy equivalent of 184 to 194 g/eq, liquid)

*3) JER807: manufactured by Mitsubishi Chemical Co., Ltd. (bisphenol F-type epoxy resin, epoxy equivalent 160 to 175 g/eq, liquid)

*4) DEN431: Dow Chemical Co., Ltd. (phenol novolak type epoxy resin (polyfunctional epoxy resin))

*5) JER630: Mitsubishi Chemical Co., Ltd. (paraaminophenol type liquid epoxy resin (polyfunctional epoxy resin), epoxy equivalent 90 to 105 g/eq, liquid)

*6) ED-509S: manufactured by ADEKA Corporation (monofunctional epoxy resin, epoxy equivalent 206 g/eq)

*7) HP-4032: DIC Co., Ltd. (naphthalene type epoxy resin, epoxy equivalent 135 to 165 g/eq; semi-solid)

*8) HP-7200L: dicyclopentadiene type epoxy resin (manufactured by DIC, epoxy equivalent 250 to 280 g/eq; softening point 57 to 68° C.)

*9) HF-1M: Meiwa Kasei Co., Ltd. (phenol novolac resin)

*10) SN-485: Shin-Nitetsu Sumikin Chemical Co., Ltd. (phenol novolac resin)

*11) LA-7054: manufactured by DIC (phenol novolac resin)

*12) PT-30: Lonza Japan Co., Ltd. (phenol novolak type polyfunctional cyanate resin)

*13) HPC-8000: Active ester resin (manufactured by DIC)

*14) BMI-2300: Daiwa Kasei High School Co., Ltd.

*15) Softon 1800: Bihoku Hunka Kogyo Co., Ltd., calcium carbonate CaCO ₃ (average particle size 1.25㎛)

*16) Admatex Co., Ltd., silica SiO ₂ (D50=0.5㎛)

*17) 2MZ-AP: Shikoku Kasei High School Co., Ltd.

*18) 2E4MZ

*19) DMAP: 4-dimethylaminopyridine

*20) FX-293: Shin-Nitetsu Sumikin Chemical Co., Ltd. (phenoxy resin)

As shown in the above table, the composition of each Example using the bisphenol E-type epoxy resin as the epoxy resin has high Tg and low CTE, low water absorption, excellent through-hole fillability, TCT resistance, abrasiveness, and voids. It was confirmed that it is possible to suppress the occurrence of

Moreover, with respect to the liquid resin composition, in Example 2 which used calcium carbonate and silica together as a filler, compared with Example 1 using only calcium carbonate, it turns out that CTE falls more and TCT resistance is improved. (A) Examples 3 to 5 in which a small amount of a bisphenol A epoxy resin and a bisphenol F epoxy resin were added to a bisphenol E-type epoxy resin. Examples 5 to 8 in which storage stability was improved and an aminophenol-type epoxy resin was added. In comparison with Example 1 in which component (A) was used alone, it can be seen that Tg is improved and heat resistance is further improved.

In addition, in Example 10 in which a solid epoxy resin was used together with the component (A) compared to Example 9 in which (A) a bisphenol E-type epoxy resin and a semi-solid epoxy resin were used together as an epoxy resin with respect to the dry film, , Tg is higher, TCT resistance is improved, and (A) Example 11 in which a semi-solid epoxy resin and a solid epoxy resin were used together with the bisphenol E-type epoxy resin was excellent also in flexibility. In Examples 12, 15 to 18, in which the liquid epoxy resin was replaced with a combination of the E-type and A-type and F-type ones of the component (A) from the formulation of Example 11, the CTE decreases by including the A-type, and storage The stability was also excellent, and in Example 13 in which the amount of silica was increased, the CTE was further decreased. Further, from the blending of Example 11, in Example 14 in which silica was replaced with calcium carbonate, the abrasiveness was further improved. Moreover, also in Example 19 in which the coloring agent was added to the formulation of Example 11, the performance equivalent to Example 11 was obtained, and in Example 20 to which the bismaleimide resin was added, Tg is further improved. Further, in Examples 21 and 22 in which the curing agent and the curing accelerator were replaced with those having no hydroxyl group from the formulation of Example 11, the water absorption was improved.

On the other hand, with respect to the liquid resin composition, in Comparative Example 1 in which only A type was used as the epoxy resin, the viscosity increased and the filling property was lowered, and it was also inferior in the point of preventing the occurrence of voids, Comparison using only F type In Example 2, Tg fell and TCT tolerance deteriorated, and in Comparative Example 3 which used A-type and F-type together, fillability fell, while being inadequate also in the point of generation|occurrence|production of a void generation|occurrence|production prevention, Tg falls and TCT resistance This is getting worse. Further, in Comparative Example 4 in which only the aminophenol type was used as the epoxy resin, the water absorption deteriorated and voids were generated, and the abrasiveness was also deteriorated. , and in Comparative Example 6 in which the phenol novolak type and the aminophenol type were used together, the water absorption deteriorated, voids were generated, and the abrasiveness was also deteriorated. Moreover, as an epoxy resin, in the comparative example 7 which used A-type and a monofunctional epoxy resin together, Tg falls and TCT tolerance is worsening.

Further, with respect to the dry film, as the epoxy resin, in Comparative Example 8 using only A-type, flexibility was lowered, and in Comparative Example 9 using only F-type, Tg decreased and TCT resistance was deteriorated, and A-type In Comparative Example 10 in which and F type were used in combination, Tg was lowered and TCT tolerance was deteriorated. In addition, among Comparative Examples 11 and 12 in which a liquid epoxy resin was not blended as an epoxy resin, in Comparative Example 11 with a small amount of residual solvent, flexibility and filling properties were lowered, and in Comparative Example 12 with a large amount of residual solvent, voids were generated, have.

1: substrate
2: copper foil
3: Through hole
4: plating film
5: resin composition
6: etching resist
7: conductor circuit layer
8: interlayer resin insulating layer
9: opening
10: plating resist layer
11: Buyer Hall
12 : Land
13: solder resist layer
14 : Solder Bump
30a: test tube for liquid determination
30b: test tube for temperature measurement
31: Marked line (A line)
32: marked line (B line)
33a, 33b: rubber stopper
34: thermometer
X: laminated board
101: insulating substrate
103: inner layer conductor pattern
103a: connection part
104, 109: resin insulating layer
108: outer layer conductor pattern
110: outermost layer conductor pattern
120: through hole
121: through hole hole
122: connection part

Claims (12)

(A) a bisphenol E-type epoxy resin;
(B) either or both of a curing agent and a curing accelerator;
(C) a non-metal filler;
Bisphenol A epoxy resin and bisphenol F epoxy resin are contained, The insulating thermosetting resin composition characterized by the above-mentioned. The insulating thermosetting resin composition according to claim 1, which does not contain a solvent. The insulating thermosetting resin composition according to claim 1, which does not contain a semi-solid epoxy resin and a solid epoxy resin. The insulating thermosetting resin composition according to claim 1, wherein the curing agent includes at least one of a phenol resin, an active ester resin, and a cyanate ester resin. The insulating thermosetting resin composition according to claim 1, which is used for manufacturing a printed wiring board. The insulating thermosetting resin composition according to claim 1, wherein the (C) non-metal filler contains either or both of calcium carbonate and silica. The insulating thermosetting resin composition according to any one of claims 1 to 6, which is used as an interlayer insulating material for a printed wiring board, a solder resist, a coverlay, or a hole filling application. It has a resin layer obtained by apply|coating and drying the insulating thermosetting resin composition of Claim 1 on a film, The dry film characterized by the above-mentioned. The dry film according to claim 8, wherein the residual solvent in the resin layer is less than 1% by mass based on the total amount of the resin layer including the solvent. It is obtained by hardening the said resin layer of the insulating thermosetting resin composition of Claim 1, or the dry film of Claim 8 or 9, The hardened|cured material characterized by the above-mentioned. It has the hardened|cured material of Claim 10, The printed wiring board characterized by the above-mentioned. delete

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