JP6268310B2 - Insulating thermosetting resin composition, dry film, cured product, and printed wiring board - Google Patents

Description

  The present invention relates to a thermosetting resin composition (hereinafter, also simply referred to as “composition”), a dry film, a cured product, and a printed wiring board. The present invention relates to a thermosetting resin composition, a dry film, a cured product, and a printed wiring board.

  In recent years, as a method for manufacturing a multilayer printed wiring board, a build-up manufacturing technique in which a resin insulating layer and a conductor layer are alternately stacked on a conductor layer of an inner circuit board has attracted attention. For example, a multilayer printed wiring board in which an epoxy resin composition is applied to a circuit-formed inner layer circuit board, heat-cured, a roughened surface is formed on the surface with a roughening agent, and a conductor layer is formed by plating Has been proposed (see Patent Document 1 and Patent Document 2). Also, after laminating an adhesive sheet of an epoxy resin composition on a circuit-formed inner layer circuit board and heat-curing it, a roughening surface is formed on the surface with a roughening agent, and a conductor layer is formed by plating A method for manufacturing a printed wiring board has been proposed (see Patent Document 3).

  Here, an example of a method for forming a layer structure of a multilayer printed wiring board by a conventional build-up method will be described with reference to FIG. First, the outer layer conductor pattern 108 is formed on both surfaces of the multilayer substrate X in which the inner layer conductor pattern 103 and the resin insulating layer 104 are previously formed on both surfaces of the insulating substrate 101, and an insulating resin such as an epoxy resin composition is formed thereon. The composition is provided by coating or the like, and cured by heating to form the resin insulating layer 109. Next, through holes 121 and the like are provided as appropriate, a conductor layer is formed on the surface of the resin insulating layer 109 by electroless plating, etc., and then a predetermined circuit pattern is formed on the conductor layer according to a conventional method. A pattern 110 can be formed. In the figure, reference numeral 103a denotes a connection part, 120 denotes a through hole, and 122 denotes a connection part.

  As one of the methods for forming a resin insulation layer (hereinafter also referred to as “interlayer insulation layer”) provided between layers in a multilayer printed wiring board, as described in Patent Document 3, thermosetting of an epoxy resin composition or the like A method is used in which a dry film having a resin layer obtained by applying and drying a conductive resin composition on a film is thermally cured after lamination. As a resin composition applied to manufacture of such a multilayer printed wiring board, for example, Patent Document 4 discloses a combination of a plurality of epoxy resins including a bisphenol A type epoxy resin and a bisphenol F type epoxy resin. ing.

  On the other hand, in a multilayer printed wiring board, it is desired to develop a permanent hole filling composition for filling recesses and through holes such as through holes and via holes. In general, as a permanent hole filling composition for a printed wiring board, a thermosetting epoxy resin composition is widely used, and the permanent filling process for a printed wiring board using such a resin composition is usually performed by an epoxy. The step of filling the hole of the printed wiring board with the resin composition, the step of pre-curing the filled composition so as to be polished, and the surface of the hole of the pre-cured resin composition protruding from the hole This is performed by a step of polishing and removing the portion and a step of further heating and pre-curing the precured resin composition. As an epoxy resin composition for hole filling of a printed wiring board, one that does not substantially contain a solvent is used, and for example, there are those disclosed in Patent Documents 5 and 6.

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

  As described above, epoxy resin compositions are used in various applications. However, a composition containing an epoxy resin that has been conventionally used has a problem that when it is in the form of a dry film, the flexibility of the dry film is lowered. Moreover, the hardened | cured material obtained from the composition containing the liquid epoxy resin used conventionally also had the problem that a glass transition temperature is comparatively low or a void tends to generate | occur | produce.

  Then, the objective of this invention is providing the thermosetting resin composition, dry film, hardened | cured material, and printed wiring board which solve the said subject and are provided with the performance more superior than before.

  As a result of intensive studies, the present inventors have found that the above-mentioned problems can be solved by using a bisphenol E type epoxy resin that has not been conventionally used as an epoxy resin, and have completed the present invention.

  That is, the thermosetting resin composition of the present invention contains (A) a bisphenol E type epoxy resin, (B) one or both of a curing agent and a curing accelerator, and (C) a filler. It is characterized by.

  The composition of the present invention is suitably used for production of a printed wiring board, and in particular, is suitably used for any of interlayer insulating materials, solder resists, coverlays, or hole filling applications for printed wiring boards. The composition of the present invention can be free of solvent depending on the application, and can also be free of semi-solid epoxy resin and solid epoxy resin. The composition of the present invention may contain at least one of a phenol resin, an active ester resin, and a cyanate ester resin as the curing agent depending on the use, and further, a bisphenol A type epoxy resin. And a bisphenol F-type epoxy resin. Moreover, in the composition of this invention, it is preferable that the said (C) filler contains either one or both of calcium carbonate and a silica.

  The dry film of the present invention is characterized by having a resin layer obtained by applying and drying the thermosetting resin composition of the present invention on the film. 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% on the resin layer whole quantity basis 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 the present invention is characterized by having the cured product of the present invention.

  According to the present invention, the flexibility of a dry film is good, the glass transition temperature of the cured product is higher than that of a cured product obtained from a liquid epoxy resin-containing composition that has been used conventionally, and thermosetting is less likely to generate voids. A resin composition, a dry film, a cured product, and a printed wiring board can be realized.

It is a fragmentary sectional view which shows schematic structure of the multilayer printed wiring board produced by the conventional buildup method. It is a schematic side view which shows the two test tubes used for the liquid determination of the epoxy resin. It is a schematic sectional drawing which shows an example of a part of manufacturing process of the printed wiring board of this invention. It is a schematic sectional drawing which shows an example of the process after 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.

Hereinafter, embodiments of the present invention will be described in detail.
In addition, in this specification, (meth) acrylate is a term which generically refers to acrylate, methacrylate and a mixture thereof, and the same applies to other similar expressions.

The thermosetting resin composition of the present invention is characterized in that it contains (A) a bisphenol E type epoxy resin, (B) one or both of a curing agent and a curing accelerator, and (C) a filler. It is what has. A thermosetting resin composition having superior performance compared to the case of using various general-purpose epoxy resins by using a bisphenol E-type epoxy resin that has not been conventionally used as an epoxy resin. And became possible. The thermosetting resin composition of the present invention is useful for the production of printed wiring boards, and is particularly suitably used for interlayer insulation materials, solder resists, and hole filling applications for printed wiring boards.
Since the composition of this invention is excellent in storage stability, it can be made into the 1 liquid type which mixed all the components. Of course, the composition of the present invention may be a two-component type in which the component (A) and the component (B) are separated.

[(A) Bisphenol E type epoxy resin]
The bisphenol E type epoxy resin has a skeleton represented by the following structural formula, is liquid at room temperature, and has a low viscosity and a low viscosity compared to bisphenol A type epoxy resin and bisphenol F type epoxy resin having a similar structure. It has the feature of having high heat resistance. In other words, the bisphenol A type epoxy resin is equivalent to the E type in terms of heat resistance, but has a high viscosity, whereas the bisphenol F type epoxy resin has a relatively low viscosity but has a disadvantage of low heat resistance. It can be said that the bisphenol E type epoxy resin has the advantages of the A type and the F type. As the bisphenol E type epoxy resin, for example, EPOX-MK R710, R1710 manufactured by Printec Co., Ltd. can be used.

  For example, when using the resin composition used for an interlayer insulation material and a soldering resist as a dry film especially, in order to maintain the softness | flexibility of a film, it is necessary to use a liquid epoxy resin as a resin component. Furthermore, in order to improve the curing characteristics of the resin composition, a method of using semi-solid and solid epoxy resins with a minimum amount of liquid epoxy resin used can be considered, but conventional bisphenol A type epoxy resins When is used, the flexibility of the film becomes insufficient, causing problems such as resin powder falling off and cracking. On the other hand, when the bisphenol F type epoxy resin was used, the heat resistance was insufficient. Therefore, when the flexibility of the film is insufficient, a method of increasing the residual solvent amount of the film has been conventionally used to increase the flexibility. However, if the residual solvent amount is large, voids (swelling There has been a problem that bubbles are easily generated.

  On the other hand, the composition of the present invention using (A) bisphenol E type epoxy resin as an epoxy resin has a lower viscosity than the case where bisphenol A type epoxy resin is used, and more than the case where bisphenol F type epoxy resin is used. Also increases heat resistance. Moreover, the flexibility of the film equivalent to the case where a bisphenol F type epoxy resin is used can be obtained. Thereby, since the amount of residual solvents can be reduced, the problem of void generation can be solved. Also, by eliminating the problem of voids by reducing the amount of residual solvent in the dry film, it is usually possible to use the dry film for filling holes used in the form of a solvent-free liquid resin composition, In the production of a printed wiring board, all of the interlayer insulating material, solder resist, and hole filling can be performed with one kind of dry film. In other words, the solder resist layer was conventionally formed after hole filling, but these can be performed simultaneously in one process, and a high-quality substrate with reduced voids can be obtained while simplifying the process and reducing costs. Became possible.

  On the other hand, for example, a resin composition used for filling a hole such as a through hole is usually used as a liquid resin composition (filling ink). Therefore, a liquid epoxy resin is widely used to make a paste without solvent. It is used. However, bisphenol A type epoxy resin has high viscosity and sufficient printability cannot be obtained, bisphenol F type epoxy resin has low heat resistance and is easily cracked, and aminophenol type epoxy resin has high water absorption and is hardened. Because of its high speed, voids are likely to remain, and since it is hard, it has poor polishing properties. In addition to its high water absorption rate, phenolic novolac type epoxy resins have high viscosity and sufficient printability, and monofunctional epoxy resins have heat resistance. Low and easy to crack, none of them was sufficient.

On the other hand, in the composition of the present invention using (A) bisphenol E type epoxy resin as an epoxy resin, in addition to being able to achieve both low viscosity and high heat resistance, bubbles are easily removed during printing and generation of voids is suppressed. Further, since the filler can be highly filled, the CTE can be further reduced, and further, since it has the same flexibility as the F type, it has excellent polishing properties.
Furthermore, in the composition of this invention, it turned out that storage stability becomes unexpectedly favorable by the combination of (A) bisphenol E type epoxy resin, bisphenol A type epoxy resin, and bisphenol F type epoxy resin. . In addition, the combination of (A) bisphenol E type epoxy resin and aminophenol type epoxy resin improves Tg and provides excellent heat resistance. (A) When using bisphenol A type epoxy resin and bisphenol F type epoxy resin in addition to bisphenol E type epoxy resin, these compounding ratios are bisphenol A type epoxy resin / bisphenol F type epoxy resin (mass ratio) = 0. .1 to 10.0.
And in the composition for 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. Furthermore, it is preferable that a semi-solid or solid epoxy resin is not included from the viewpoint of filling into the hole.

[(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.

(Curing agent)
Examples of the curing agent include phenol resins, polycarboxylic acids and acid anhydrides thereof, cyanate ester resins, and active ester resins. A hardening | curing agent can be used individually by 1 type or in combination of 2 or more types.

  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, polyvinylphenols, phenol / naphthol resin, Conventionally known ones such as an α-naphthol skeleton-containing phenol resin and a triazine-containing cresol novolak resin can be used singly or in combination of two or more.

  The polycarboxylic acid and acid anhydride thereof are compounds having two or more carboxyl groups in one molecule and acid anhydrides thereof, such as a copolymer of (meth) acrylic acid and a copolymer of maleic anhydride. In addition to condensates of dibasic acids, resins having a carboxylic acid end such as a carboxylic acid-terminated imide resin can be mentioned.

  The cyanate ester resin is a compound having two or more cyanate ester groups (—OCN) in one molecule. Any conventionally known cyanate ester resins can be used. Examples of the cyanate ester resin include phenol novolac type cyanate ester resin, alkylphenol novolak type cyanate ester resin, dicyclopentadiene type cyanate ester resin, bisphenol A type cyanate ester resin, bisphenol F type cyanate ester resin, and bisphenol S type cyanate ester resin. Is mentioned. Further, it may be a prepolymer partially triazine.

  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 between a carboxylic acid compound and a hydroxy compound. Among these, an active ester compound obtained by using a phenol compound or a naphthol compound as the hydroxy compound is preferable. Examples of phenol compounds or naphthol compounds include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, 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, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol , Dicyclopentadienyl diphenol, phenol novolac and the like.

  Moreover, you may use an alicyclic olefin polymer as a hardening | curing agent. Specific examples of the method for producing an alicyclic olefin polymer include (1) an alicyclic olefin having a carboxyl group and / or a carboxylic acid anhydride group (hereinafter referred to as “carboxyl group etc.”) as necessary. (2) The aromatic ring portion of the (co) polymer obtained by polymerizing an aromatic olefin having a carboxyl group or the like with another monomer as necessary. (3) a method of copolymerizing an alicyclic olefin having no carboxyl group and a monomer having a carboxyl group, (4) an aromatic olefin having no carboxyl group, and a carboxyl group A method of hydrogenating an aromatic ring portion of a copolymer obtained by copolymerizing with a monomer having, for example, (5) an alicyclic olefin polymer having no carboxyl group or the like having a carboxyl group or the like. Or a carboxylic acid ester group of an alicyclic olefin polymer having a carboxylic acid ester group obtained as described in (1) to (5) above, for example, The method etc. which convert to a carboxyl group by decomposition | disassembly etc. are mentioned.

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

  The ratio of the epoxy group of the epoxy resin containing the (A) bisphenol E type epoxy resin and the functional group in the curing agent that reacts with the epoxy group is equal to the functional group / epoxy group of the curing agent (equivalent ratio). ) = 0.2 to 2.0 is preferably blended at such a ratio. By setting the functional group / epoxy group (equivalent ratio) of the curing agent within the above range, roughening of the film surface in the 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. is there.

(Curing accelerator)
The curing accelerator is for accelerating the thermosetting reaction, and is used for further improving properties such as adhesion, chemical resistance, and heat resistance. Specific examples of such curing accelerators include imidazole and derivatives thereof; guanamines such as acetoguanamine and benzoguanamine; diaminodiphenylmethane, m-phenylenediamine, m-xylenediamine, diaminodiphenylsulfone, dicyandiamide, urea, urea derivatives, Polyamines such as melamine and polybasic hydrazides; organic acid salts and / or epoxy adducts thereof; amine complexes of boron trifluoride; ethyldiamino-S-triazine, 2,4-diamino-S-triazine, 2,4- Triazine derivatives such as diamino-6-xylyl-S-triazine; trimethylamine, triethanolamine, N, N-dimethyloctylamine, N-benzyldimethylamine, pyridine, N-methylmorpholine, hexa (N-methyl) Amines such as lamin, 2,4,6-tris (dimethylaminophenol), tetramethylguanidine, m-aminophenol; polyphenols such as polyvinylphenol, polyvinylphenol bromide, phenol novolac, alkylphenol novolac; tributylphosphine, tri Organic phosphines such as phenylphosphine and tris-2-cyanoethylphosphine; phosphonium salts such as tri-n-butyl (2,5-dihydroxyphenyl) phosphonium bromide and hexadecyltributylphosphonium chloride; benzyltrimethylammonium chloride and phenyltributylammonium chloride Quaternary ammonium salts such as polybasic acid anhydrides; diphenyliodonium tetrafluoroboroate, triphenyl Photocationic polymerization catalyst such as sulfonium hexafluoroantimonate and 2,4,6-triphenylthiopyrylium hexafluorophosphate; styrene-maleic anhydride resin; equimolar reaction product of phenyl isocyanate and dimethylamine, tolylene diisocyanate, Conventionally known curing accelerators such as an equimolar reaction product of an organic polyisocyanate such as isophorone diisocyanate and dimethylamine, and a metal catalyst can be used. Among the curing accelerators, phosphonium salts are preferred because BHAST resistance is obtained.

Moreover, when using the composition of this invention as a liquid resin composition for hole filling, an imidazole derivative is especially preferable. Specific examples of the imidazole derivative include, for example, 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-methylimidazole, 1-cyanoethyl-2-undecylimidazole and the like. Specific examples of commercially available products include imidazoles such as trade names 2E4MZ, C11Z, C17Z, and 2PZ, AZINE compounds of imidazoles such as trade names 2MZ-A and 2E4MZ-A, trade names 2MZ-OK, and 2PZ-OK. And imidazole hydroxymethyl compounds such as trade names 2PHZ and 2P4MHZ (the trade names are all 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, triethanolamine, diaminodiphenylmethane, organic acids Amines such as hydrazide, 1,8-diazabicyclo [5.4.0] undecene-7 (trade name DBU, manufactured by San Apro), 3,9-bis (3-aminopropyl) -2,4,8 , 10-tetraoxaspiro [5.5] undecane (trade name ATU, manufactured by Ajinomoto Co., Inc.) or organic phosphine compounds such as triphenylphosphine, tricyclohexylphosphine, tributylphosphine, methyldiphenylphosphine alone Also It can be used in combination of two or more. However, when aromatic amines are used, the resin composition after heat-curing shrinks greatly, and a gap is likely to form between the through-hole wall after curing and voids are likely to occur in the cured product in the hole filling portion. Absent. Among these curing catalysts, dicyandiamide, melamine, acetoguanamine, benzoguanamine, 3,9-bis [2- (3,5-diamino-2,4,6-triazaphenyl) ethyl] -2,4,8 , 10-tetraoxaspiro [5.5] undecane and derivatives thereof, and their organic acid salts and epoxy adducts are known to have adhesion and rust prevention properties with copper. In addition to acting as a curing catalyst for the resin, it can contribute to the prevention of discoloration of copper in the 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 can be preferably used in 0.01-20 mass parts with respect to 100 mass parts of epoxy resins containing (A) bisphenol E type epoxy resin. Moreover, in the case of a metal catalyst, 10-550 ppm is preferable at metal conversion with respect to 100 mass parts of (A) 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 blending the filler, the curing characteristics can be improved by bringing the conductor layer such as copper around the insulating layer closer to the CTE. As the filler, any conventionally known inorganic filler and organic filler can be used, and the filler is not limited to a specific one. However, it suppresses curing shrinkage of the coating film and contributes to improvement of properties such as adhesion and hardness. An inorganic filler that can be used is preferred. Examples of inorganic fillers 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, and aluminum nitride. Boron nitride, alumina, magnesium oxide, magnesium hydroxide, titanium oxide, mica, talc, Neuburg silica, organic bentonite, zirconium phosphate and other non-metallic fillers, copper, tin, zinc, nickel, silver, palladium, aluminum Examples thereof include metal fillers such as iron, cobalt, gold, platinum, and silicon. One kind can be used alone, or two or more kinds can be used in appropriate combination.

  In the present invention, among the above, it is preferable to use one or both of calcium carbonate and silica as the filler (C). By blending calcium carbonate, a dry film having flexibility and excellent polishing properties can be obtained, and by blending silica, CTE can be further reduced and TCT resistance can be improved. Silica may be either amorphous or crystalline, or a mixture thereof. In particular, amorphous (fused) silica is preferred. The calcium carbonate may be any of natural heavy calcium carbonate and synthetic precipitated calcium carbonate. In particular, when the composition of the present invention is used for filling a hole, it is preferable to use calcium carbonate having excellent polishing properties as the filler (C).

  Examples of the shape of the filler include a spherical shape, a needle shape, a plate shape, a scale shape, a hollow shape, an indefinite shape, a hexagonal shape, a cubic shape, and a flaky shape. From the viewpoint of high filling with an inorganic filler, a spherical shape is preferable. . Further, the average particle size of the filler is preferably 25 μm or less, and more preferably 5 μm or less. As a lower limit, it is 1 nm or more, for example. On the other hand, when it is 25 μm or less, when the composition of the present invention is used as a hole-filling material, the filling property into the hole of the printed wiring board is improved, and when the conductor layer is formed in the hole-filled portion, it is smooth. There is an effect of improving the nature. The average particle size can be determined by a laser diffraction particle size distribution measuring device.

  The blending amount of the (C) filler in the composition of the present invention is preferably from 1 to 90% by mass, more preferably from 10 to 90% by mass, based on the total amount of the composition excluding the solvent, from 30 to 30%. More preferably, it is 80 mass%. When the blending amount of the filler is 1% by mass or more, thermal expansion can be suppressed, heat resistance can be improved, and polishing properties and adhesion can be exhibited. On the other hand, when the content is 90% by mass or less, the hardness of the cured product is improved, cracks can be suppressed, liquid paste is easily formed, and printability, hole filling, and the like are obtained.

  The composition of the present invention is required to contain the above components (A), (B) and (C), but may further contain other components depending on the application.

(Other epoxy resins)
In the composition of the present invention, it is essential to contain (A) bisphenol E type epoxy resin as an epoxy resin. However, one or two other epoxy compounds may be used as long as the desired effects of the present invention are not impaired. It may contain more than seeds.

  The epoxy compound is a compound having an epoxy group, and any conventionally known one can be used. A bifunctional epoxy compound having two epoxy groups in the molecule, a polyfunctional epoxy compound having many epoxy groups in the molecule. Etc. In addition, a hydrogenated bifunctional epoxy compound may be used.

  Examples of the epoxy compound include bisphenol A type 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 novolac type epoxy resin, and cresol novolak type. Epoxy resin, bisphenol A novolak type 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 Resin, amino cresol type epoxy resin, alkylphenol type epoxy resin or the like is used. The epoxy compound may be a solid epoxy resin, a semi-solid epoxy resin, or a liquid epoxy resin.

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

The determination of the liquid state can be performed in accordance with the second “liquid confirmation method” of the ministerial ordinance on the test and properties of hazardous materials (Ministry of Local Government Ordinance No. 1 of 1989).
(1) Equipment constant temperature water bath:
A thing equipped with a stirrer, a heater, a thermometer, and an automatic temperature controller (with temperature control at ± 0.1 ° C.) having a depth of 150 mm or more is used.
In the determination of the epoxy resin used in the examples described later, all use a combination of a low-temperature thermostatic water tank (model BU300) manufactured by Yamato Scientific Co., Ltd. and a thermostat (model BF500) of a charging type thermostatic apparatus (model BF500), and about 22 liters of tap water. Is put into a low temperature constant temperature water bath (model BU300), the thermomate (model BF500) assembled to this is turned on and set to a set temperature (20 ° C or 40 ° C), and the water temperature is set to a set temperature ± 0.1 ° C. Although fine adjustment was performed with a thermomate (model BF500), any apparatus capable of the same adjustment can be used.

Test tube:
As shown in FIG. 2, the test tube is made of a flat bottom cylindrical transparent glass having an inner diameter of 30 mm and a height of 120 mm, and marked lines 31 and 32 are respectively provided at heights of 55 mm and 85 mm from the tube bottom. The test tube 30a for liquid judgment with the test tube 30a sealed with a rubber plug 33a is the same size as that of the test tube 30a. The rubber plug 33b is similarly provided with a marked line and a hole for inserting and supporting a thermometer in the center. A test tube 30b for temperature measurement in which the mouth of the test tube is sealed and a thermometer 34 is inserted into the rubber plug 33b is used. Hereinafter, a marked line having a height of 55 mm from the tube bottom is referred to as “A line”, and a marked line having a height of 85 mm from the tube bottom is referred to as “B line”.
As the thermometer 34, the one for freezing point measurement (SOP-58 scale range 20-50 ° C) specified in JIS B7410 (1982) "Petroleum test glass thermometer" is used, but the temperature is 0-50 ° C. It is sufficient if the range can be measured.

(2) Test procedure The liquid test tube 30a shown in FIG. 2 (a) and the temperature measurement test shown in FIG. 2 (b) were prepared for 24 hours or more at atmospheric pressure of 20 ± 5 ° C. Insert up to line A in each tube 30b. The two test tubes 30a and 30b are left standing in a low temperature constant temperature water tank so that the line B is below the water surface. The thermometer has its lower end 30 mm below the A line.
The state is maintained as it is for 10 minutes after the sample temperature reaches the set temperature ± 0.1 ° C. Ten minutes later, the test tube 30a for liquid judgment is taken out of the low-temperature water bath and immediately tilted horizontally on a horizontal test stand, and the time when the tip of the liquid level in the test tube has moved from the A line to the B line is measured with a stopwatch. Measure and record. A sample is determined to be liquid when the measured temperature is 90 seconds or less at a set temperature, and solid when it exceeds 90 seconds.

  As the solid epoxy resin, HP-4700 (naphthalene type epoxy resin) manufactured by DIC, EXA4700 (tetrafunctional naphthalene type epoxy resin) manufactured by DIC, NC-7000 (polyfunctional solid epoxy resin containing naphthalene skeleton) manufactured by Nippon Kayaku Co., Ltd. Naphthalene-type epoxy resins such as EPPN-502H (trisphenol epoxy resin) manufactured by Nippon Kayaku Co., Ltd. Epoxidized products (trisphenol-type epoxy resins) of condensation products of phenols and aromatic aldehydes having a phenolic hydroxyl group; Dicyclopentadiene aralkyl epoxy resin such as Epiklon HP-7200H (dicyclopentadiene skeleton-containing polyfunctional solid epoxy resin) manufactured by Nippon Kayaku Co., Ltd .; biphenyl aralkyl such as NC-3000H (biphenyl skeleton-containing polyfunctional solid epoxy resin) manufactured by Nippon Kayaku Co., Ltd. Type Epoxy Resin; biphenyl / phenol novolak type epoxy resin such as NC-3000L manufactured by Nippon Kayaku; novolak type epoxy resin such as Epicron N660 and Epicron N690 manufactured by DIC, EOCN-104S manufactured by Nippon Kayaku; YX- manufactured by Mitsubishi Chemical Corporation Biphenyl type epoxy resin such as 4000; Phosphorus-containing epoxy resin such as TX0712 manufactured by Nippon Steel & Sumikin Chemical Co .; Tris (2,3-epoxypropyl) isocyanurate such as TEPIC manufactured by Nissan Chemical Industries, Ltd.

  Semi-solid epoxy resins include DIC Corporation Epicron 860, Epicron 900-IM, Epicron EXA-4816, Epicron EXA-4822, Asahi Ciba Araldite AER280, Toto Kasei Epoto YD-134, Japan Epoxy Resin Corporation jER834. , JER872, bisphenol A type epoxy resin such as ELA-134 manufactured by Sumitomo Chemical Co., Ltd .; naphthalene type epoxy resin such as Epicron HP-4032 manufactured by DIC; phenol novolak type epoxy resin such as Epicron N-740 manufactured by DIC It is done.

  Liquid epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, glycidylamine type epoxy resin, aminophenol type epoxy resin And alicyclic epoxy resins.

  In the composition of the present invention, a semi-solid epoxy resin and a solid epoxy resin may be used in combination with the liquid (A) bisphenol E type epoxy resin. In this case, the compounding amount of the component (A) is preferably 1 to 45% by mass, more preferably 1 to 30% by mass, more preferably 1 to 10% by mass based on the total amount of the composition in terms of solid content. % Is more preferable.

  Semi-solid or solid epoxy resins can be used singly or in combination of two or more. The compounding amount of the semi-solid and solid epoxy resins is preferably 5 to 50% by mass, more preferably 10 to 40% by mass based on the total amount of the composition in terms of solid content excluding the solvent. -35 mass% is further more preferable.

  Further, as long as the heat resistance, flexibility and water absorption can be maintained, other liquid components such as bisphenol A type epoxy resin may be used as the liquid epoxy resin together with (A) bisphenol E type epoxy resin. In this case, the blending amount of the (A) bisphenol E type epoxy resin is preferably 1 to 90% by mass, more preferably 1 to 70% by mass based on the total amount of the liquid epoxy resin, and 1 to 50%. More preferably, it is mass%.

  Moreover, when using the composition of this invention, for example as a liquid resin composition for hole filling, it is preferable to use a polyfunctional epoxy resin together with (A) bisphenol E type epoxy resin. By using a polyfunctional epoxy resin together with the component (A), there is an effect that the heat resistance can be further improved. In this case, the blending amount of the component (A) is preferably 10% by mass or more, more preferably 15 to 80% by mass, more preferably 15 to 80% by mass with respect to the total amount of the epoxy resin including the bisphenol E type epoxy resin. More preferably, it is 60 mass%.

  Furthermore, when using the composition of this invention as a liquid resin composition for hole filling, for example, you may use a solid epoxy resin dissolved in a solvent with (A) bisphenol E type epoxy resin. In this case, ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, petroleum solvents and the like can be used as the solvent. 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 , Glycol ethers such as dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether; ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, S such as propylene glycol butyl ether acetate, methyl lactate, ethyl lactate, butyl lactate Examples include 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. it can. These solvents may be used alone or in combination of two or more. In addition, what is necessary is just to determine the compounding quantity of a solvent suitably based on workability | operativity etc. in the range in which the effect of this invention is acquired.

(Coloring agent)
The composition of the present invention may contain a colorant as necessary. By containing the colorant, in particular, when the composition of the present invention is used for forming a surface layer such as a solder resist layer, the concealability of a circuit or the like can be enhanced. As the colorant, conventionally known colorants such as red, blue, green, yellow, white, and black can be used, and any of pigments, dyes, and pigments may be used. Specific examples include color index (CI; issued by The Society of Dyer's and Colorists) number. However, it is preferable that the colorant does not contain a halogen from the viewpoint of reducing environmental burden and affecting the human body.

  Examples of the red colorant include monoazo, diazo, azo lake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, and quinacridone. Examples of blue colorants include metal-substituted or unsubstituted phthalocyanine-based and anthraquinone-based compounds, and pigment-based compounds that are classified as pigments. Similarly, the green colorant includes metal-substituted or unsubstituted phthalocyanine-based, anthraquinone-based, and perylene-based materials. Examples of yellow colorants include monoazo, disazo, condensed azo, benzimidazolone, isoindolinone, and anthraquinone. Examples of the white colorant include rutile type, anatase type titanium oxide and the like. Black colorants include titanium black, carbon black, graphite, iron oxide, anthraquinone, cobalt oxide, copper oxide, manganese, antimony oxide, nickel oxide, perylene, and aniline. Examples thereof include pigments, molybdenum sulfide, and bismuth sulfide. In addition, a colorant such as purple, orange or brown may be added for the purpose of adjusting the color tone. A coloring agent can be used individually by 1 type or in combination of 2 or more types.

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

(Thermoplastic resin (polymer resin))
The composition of the present invention can further contain a thermoplastic resin in order to improve the mechanical strength of the resulting cured film. As the thermoplastic resin, use is made of thermoplastic polyhydroxy polyether resin, phenoxy resin that is a condensate of epichlorohydrin and various bifunctional phenolic compounds, or hydroxyl group of hydroxy ether part present in the skeleton of various acid anhydrides and acid chlorides. And esterified phenoxy resin, polyvinyl acetal resin, polyamide resin, polyamideimide resin, block copolymer and the like. A thermoplastic resin can be used individually by 1 type or in combination of 2 or more types. Those obtained by acylating the hydroxyl group of the phenoxy resin are preferable because of excellent electrical characteristics.

  The polyvinyl acetal resin is obtained, for example, by acetalizing a polyvinyl alcohol resin with an aldehyde. The aldehyde is not particularly limited, and examples thereof include formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, amylaldehyde, hexylaldehyde, heptylaldehyde, 2-ethylhexylaldehyde, cyclohexylaldehyde, furfural, benzaldehyde, 2-methylbenzaldehyde, 3- Examples include methylbenzaldehyde, 4-methylbenzaldehyde, p-hydroxybenzaldehyde, m-hydroxybenzaldehyde, phenylacetaldehyde, β-phenylpropionaldehyde, and the like, butyraldehyde is preferable.

  Specific examples of the phenoxy resin include FX280 and FX293 manufactured by Tohto Kasei Co., Ltd., YX8100, YX6954, YL7213, and YL7218 manufactured by Mitsubishi Chemical Corporation. Specific examples of the polyvinyl acetal resin include SLEKS KS series manufactured by Sekisui Chemical Co., Ltd., the polyamide resin includes KS5000 series manufactured by Hitachi Chemical Co., Ltd., the Nippon Kayaku BP series, and the polyamideimide resin includes Hitachi Chemical Co., Ltd. Examples include the KS9000 series.

  When a thermoplastic polyhydroxy polyether resin has a fluorene skeleton, it has a high glass transition point and excellent heat resistance. Therefore, it maintains a low coefficient of thermal expansion due to a semi-solid or solid epoxy resin and maintains its glass transition point. The resulting cured film has a low thermal expansion coefficient and a high glass transition point in a well-balanced manner. In addition, since the thermoplastic polyhydroxy polyether resin has a hydroxyl group, it exhibits good adhesion to the substrate and the conductor, and the cured film obtained is not easily affected by the roughening agent, but the aqueous solution is roughened. Since the liquid easily penetrates into the interface between the cured film and the filler, the roughening treatment makes it easy for the filler on the surface of the cured film to come off, and it becomes easy to form a good roughened surface.

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

  The block copolymer is preferably an ABA type or AB-A 'type block copolymer. Of the ABA type and ABA type block copolymers, the central B is a soft block and has a low glass transition temperature (Tg), preferably less than 0 ° C. Alternatively, it is preferable that A ′ is a hard block and has a high glass transition temperature (Tg), preferably composed of polymer units of 0 ° C. or higher. The glass transition temperature (Tg) is measured by differential scanning calorimetry (DSC). Further, among the ABA type and ABA type block copolymers, A or A ′ is composed of polymer units having a Tg of 50 ° C. or higher, and B has a glass transition temperature (Tg) of −20. More preferred is a block copolymer composed of polymer units having a temperature of 0 ° C. or lower. Further, among the ABA type and ABA type block copolymers, those in which A or A 'is highly compatible with the bisphenol E type epoxy resin are preferable, and B is the bisphenol E type. A thing with low compatibility with an epoxy resin is preferable. Thus, it is considered that a specific structure in the matrix can be easily shown 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, phenoxy resins, polyvinyl acetal resins, thermoplastic polyhydroxy polyether resins having a fluorene skeleton, and block copolymers are preferable, and phenoxy resins are 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 blending amount of the thermoplastic resin is within the above range, a uniform roughened surface state can be easily obtained.

(Maleimide compound)
The composition of the present invention can further contain a maleimide compound. By blending the maleimide compound, Tg can be further improved.

  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, and N, N′-1,3-phenylene dimaleimide, N, N′-1,4-phenylene dimaleimide, N, N′-4,4- Diphenylmethane bismaleimide, 1,2-bis (maleimido) ethane, 1,6-bismaleimide hexane, 1,6-bismaleimide- (2,2,4-trimethyl) hexane, 2,2′-bis- [4- (4-maleimidophenoxy) phenyl] propane, 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethane bismaleimide, 4-methyl-1,3-phenylenebismaleimide, bis (3-ethyl -5-methyl-4-maleimidophenyl) methane, bisphenol A diphenyl ether bismaleimide, polyphenylmethanemaleimide, And more preferably at least one kind of diamine condensates with these oligomers and maleimide skeleton. The said oligomer is an oligomer obtained by condensing the maleimide compound which is a monomer in the above-mentioned maleimide compound. A maleimide compound can be used individually by 1 type or in combination of 2 or more types.

  Among the maleimide compounds, at least one of a condensate of phenylmethanemaleimide and a bismaleimide oligomer is more preferable. The bismaleimide oligomer is preferably an oligomer obtained by condensation of phenylmethane bismaleimide and 4,4-diaminodiphenylmethane. As a commercial product of the condensate of phenylmethanemaleimide, BMI-2300 manufactured by Daiwa Kasei Co., Ltd. can be mentioned. Moreover, as a commercial item of bismaleimide oligomer, Daiwa Kasei Co., Ltd. DAIMAID-100H etc. are mentioned.

The maleimide compound is preferably 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 hydrogen atoms.

  The maleimide compound is preferably a mixture of maleimide compounds represented by the general formula (I). Moreover, since the solubility of a mixture increases and CTE of the hardened | cured material of a resin layer becomes lower, it is more preferable that the average value of n in the said general formula (I) of a mixture is 0.1-1. The higher the average value of n, the higher the solubility of the mixture. In the case of a mixture of maleimide compounds in which the average value of n is 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 the heat resistance is thin. It is also possible to use a substrate.

  The blending amount of the maleimide compound is preferably 2 to 50% by mass and more preferably 10 to 50% by mass based on the total amount of the composition excluding the solvent and filler. In the case of 2% by mass or more, the CTE of the cured product becomes low, and the Tg of the cured product 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, for example, a dry film for an interlayer insulating material and a solder resist, if necessary, conventionally known thickeners such as asbestos, olben, benton, fine silica, and silicone , Fluorine-based, polymer-based and other antifoaming agents and / or leveling agents, thiazole-based, triazole-based, silane coupling agents and other adhesion-imparting agents, flame retardants, titanate-based, aluminum-based conventionally known additives Can be used.

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

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

  Solvents 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, trichloroethylene, acetic acid. And isopropyl.

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

  Examples of the solvent having a boiling point of 100 ° C. or higher include xylene, petroleum-based naphtha, Maruzen Petrochemical Co., Ltd. Swazol 1000 (carbon number 8 to 10: high-boiling aromatic hydrocarbon), and swazole 1500 (high-boiling aromatic hydrocarbon). Solvesso 100 (carbon number 9 to 10: high boiling aromatic hydrocarbon), Solvesso 150 (carbon number 10 to 11: high boiling aromatic hydrocarbon), Sankyo Chemical Co., Solvent # 100, Solvent # 150, Shellsol A100 manufactured by Shell Chemicals Japan, Shellsol A150, Ipsol 100 manufactured by Idemitsu Kosan Co., Ltd. (mainly aromatic hydrocarbons having 9 carbon atoms), No. 150 Ipsol (aromatic hydrocarbons having 10 carbon atoms) Is a main component). The high-boiling aromatic hydrocarbon preferably contains 99% by volume or more of an aromatic component. Moreover, it is preferable that each of high-boiling aromatic hydrocarbons is less than 0.01% by volume of benzene, toluene and xylene.

  When forming a dry film using the composition of this invention, you may mix | blend 3 or more types of solvents with a boiling point of 100 degreeC or more in a composition, In this case, any one of 3 or more types of solvents. Any solvent may be used as long as the two solvents have different boiling points. Among solvents having a boiling point of 100 ° C. or higher, solvents having a boiling point of 100 to 230 ° C. are preferable, and solvents having a boiling point of 100 to 220 ° C. are more preferable. When the boiling point is 230 ° C. or lower, the solvent hardly remains in the resin layer of the dry film after the thermosetting or annealing treatment. Such a solvent is more preferably toluene, N, N-dimethylformamide, methoxypropanol, methyl isobutyl ketone, cyclohexanone, petroleum naphtha, or aromatic hydrocarbon having 8 or more carbon atoms. Among these, a combination of toluene and cyclohexane, a combination of toluene and methyl isobutyl ketone, and a combination of cyclohexanone and methyl isobutyl ketone are more preferable.

  The amount of the solvent before drying is preferably 10 to 150 parts by mass and more preferably 25 to 100 parts by mass with respect to 100 parts by mass of the resin layer of the dry film excluding the solvent. When the compounding amount of the solvent is 10 parts by mass or more, the solubility is improved and the amount of the residual solvent is easily adjusted. On the other hand, when it is 150 parts by mass or less, the thickness of the resin layer is easily controlled.

  The composition of the present invention can also be applied as a liquid resin composition to the formation of a cured film on a printed wiring board such as an interlayer insulating material, a coverlay or a solder resist.

(Other ingredients)
When the composition of the present invention is used, for example, as a liquid resin composition for filling holes, if necessary, in order to impart storage stability during storage, a boric acid ester compound, hydroquinone, hydroquinone monomethyl ether, Known and conventional thermal polymerization inhibitors such as tert-butylcatechol, pyrogallol and phenothiazine, known and commonly used thickeners or thixotropic agents such as clay, kaolin, organic bentonite and montmorillonite, silicones, fluorines and polymers Known and commonly used additives such as a foaming agent and / or a leveling agent, an adhesion-imparting agent such as an imidazole-based, thiazole-based, triazole-based, and silane coupling agent can be added. In particular, when organic bentonite is used, a portion protruding from the surface of the hole is easily formed in a protruding state that can be easily polished and removed, and is excellent in polishing properties.
The thermosetting resin composition of the present invention can obtain excellent cured product characteristics by heating. Therefore, the thermosetting resin composition of the present invention does not need to contain a component such as a photopolymerizable monomer that is itself polymerized by light irradiation.

[Form of composition]
The form of the composition of the present invention may be provided as a liquid resin composition having a moderately adjusted viscosity. As described above, a dry film obtained by applying the composition onto a supporting base film and drying the solvent. It is good. Moreover, it is good also as a prepreg sheet | seat which apply | coated and / or impregnated the sheet-like fibrous base materials, such as a glass cloth, glass, and an aramid nonwoven fabric, and was semi-hardened. Examples of the supporting base film include polyolefins such as polyethylene and polyvinyl chloride, polyesters such as polyethylene terephthalate, polycarbonates and polyimides, and metal foils such as release paper, copper foil, and aluminum foil. Note that the support base film may be subjected to a release treatment in addition to the mud treatment and the corona treatment.

  The liquid resin composition, dry film, or prepreg using the composition of the present invention is directly coated on the inner circuit board on which the circuit is formed, and dried or cured, or the dry film is laminated by heating to be integrated. It may be molded and then cured in an oven or hot plate press. In the case of a prepreg, a method of stacking on an inner layer circuit board, sandwiching it with a metal plate via a release film, and pressurizing and heating can be used.

  Among the above steps, the method of laminating or hot plate pressing is preferable because the fine unevenness caused by the inner layer circuit is eliminated when heated and melted and is cured as it is, so that a multilayer plate having a flat surface state can be finally obtained. Moreover, when laminating or hot plate pressing the base material on which the inner layer circuit is formed and the film or prepreg of the composition of the present invention, the copper foil or the base material on which the circuit is formed can be simultaneously laminated.

A hole is made in the substrate thus obtained with a semiconductor laser such as a CO ₂ laser or a UV-YAG laser or a drill. The hole is a through hole (through hole) that is intended to connect the front and back of the substrate, but it is also a partial hole (conformal via) that is intended to connect the inner layer circuit and the circuit on the surface of the interlayer insulating layer. either will do.

  After drilling, in order to remove the residue (smear) present on the inner wall and bottom of the hole and to develop an anchor effect with the conductor layer (the metal plating layer to be formed thereafter), a rough surface with fine irregularities For the purpose of forming a chemical surface, a commercially available desmear liquid (roughening agent) or a roughening liquid containing an oxidizing agent such as permanganate, dichromate, ozone, hydrogen peroxide / sulfuric acid, nitric acid, etc. Do it at the same time.

  Next, a circuit is formed by a subtractive method, a semi-additive method, or the like after forming a hole from which a residue has been removed with a desmear liquid or a film surface having a fine uneven rough surface. In either method, after electroless plating or electrolytic plating, or after both plating, a heat treatment called annealing at about 80 to 200 ° C. for about 10 to 60 minutes for the purpose of removing stress from the metal and improving the strength. May be applied.

  As metal plating used here, there is no restriction | limiting in particular, such as copper, tin, solder, nickel, etc., It can also be used in multiple combination. Further, instead of the plating used here, metal sputtering or the like can be used instead.

  The composition of the present invention can be suitably used for the production of a printed wiring board, in particular, the formation of an insulating layer of a printed wiring board such as an interlayer insulating layer or a solder resist, and the filling of holes such as through holes and via holes Can be suitably used.

[Dry film]
The dry film of the present invention can be produced by applying the composition of the present invention on a carrier film and drying to form a resin layer as a dry coating film. A protective film can be laminated on the resin layer as necessary.

  As a material of the carrier film, polyethylene terephthalate (PET) or the like can be preferably used. The thickness of the carrier film is preferably 8 to 75 μm. Moreover, as a material of a protective film, the thing similar to what is used for a carrier film can be used, Preferably it is PET or polypropylene (PP). The thickness of the protective film is preferably 5 to 50 μm. In the present invention, a resin layer may be formed by applying and drying the composition of the present invention on the protective film, and a carrier film may be laminated on the surface. That is, as a film to which the composition of the present invention is applied when producing a dry film in the present invention, either a carrier film or a protective film may be used.

  Here, as a coating method of the composition, a dip coating method, a flow coating method, a roll coating method, a bar coater method, a screen printing method, a curtain coating method, or the like can be used. Also, as the volatile drying method, a hot air circulation drying furnace, an IR (infrared) furnace, a hot plate, a convection oven, or the like equipped with a heat source of an air heating method using steam can be used.

  In the dry film of the present invention, the residual solvent amount of the resin layer formed as described above is preferably less than 1% by mass based on the total amount of the resin layer including the solvent, and is 0.01 to 0.8. More preferably, it is mass%. By setting the amount of residual solvent in the resin layer within the above range, it is possible to improve the releasability, reduce the residual of bubbles and suppress the generation of cracks more effectively while suppressing the cracking and powder falling of the dry film. Will be able to.

[Composition for filling holes]
When the composition of the present invention is used as a liquid resin composition for filling holes, a conventionally employed method, for example, a screen printing method, a roll coating method, a die coating method, or the like is used. Holes such as via holes and through holes can be easily filled. Next, for example, the composition is cured by heating at about 90 to 180 ° C. for about 30 to 90 minutes. Next, in the cured composition, the unnecessary portion protruding from the substrate surface can be easily removed by physical polishing, and a flat surface can be obtained. The physical polishing can be performed by a known method that has been conventionally performed.

[Hardened products and printed wiring boards]
The cured product of the present invention is obtained by curing the resin layer of the composition or dry film of the present invention, and the printed wiring board of the present invention comprises the cured product of the present invention. Although the manufacturing method is demonstrated below, it is not limited to this.

[Manufacture of printed wiring boards]
Production of a printed wiring board using the composition of the present invention can be performed, for example, as shown in FIGS. In the example shown in FIG. 3, first, a through hole is formed in the substrate 1 laminated with the copper foil 2, and electroless plating is performed on the wall surface and the copper foil surface to form the through hole 3 (FIG. 3A). Then, a plating film 4a is formed on the surface of the substrate 1 and the inner wall of the through hole 3 (FIG. 3B). Next, after filling the through-hole 3 with the liquid resin composition 5 using the composition of the present invention (FIG. 3 (c)) and heat-curing, the unnecessary portion protruding from the through-hole 3 is polished. Planarization is performed (FIG. 3D). Next, after forming the plating film 4b on the surface of the substrate 1 (FIG. 3E), an etching resist 6 is formed (FIG. 3F), and the etching resist 6 is removed by etching the non-resist forming portion. Thus, the conductor circuit layer 7a is formed (FIG. 3G).

  Next, an interlayer insulating layer 8a is formed on the conductor circuit layer 7a by a dry film using the composition of the present invention, and an opening 9a is provided (FIG. 4A). Next, a plating film 4c is formed on the entire surface (FIG. 4 (b)), and after forming a plating resist layer 10 on the plating film 4c, further electrolytic plating is performed to thicken the conductor circuit portion and electrolytic plating. A film 4d is formed (FIG. 4C). Next, after the plating resist layer 10 is peeled off, the electroless plating film 4c thereunder is dissolved and removed by etching to form independent conductor circuits (including via holes 11a) (FIG. 4D).

  In another example shown in FIG. 5, after finishing the core substrate manufacturing process shown in FIG. 3D, the conductor layers on both surfaces of the core substrate 1 are etched to form the first conductor circuit on both surfaces of the substrate 1. The layer 7b is formed, and the land 12 is formed on a part of the conductor circuit layer 7b connected to the through hole 3 (FIG. 5A). Next, an interlayer insulating layer 8b is formed on both upper and lower surfaces of the substrate 1 (FIG. 5B), and a via hole 11b is formed in the interlayer insulating layer 8b located directly above the land 12 (FIG. 5C). )). Next, a plating layer is formed in the via hole 11b and on the interlayer insulating layer 8b, an etching resist is formed thereon, and etching is performed to form the second conductor circuit layer 7c on the interlayer insulating layer 8b. It forms (FIG.5 (c)). The first and second conductor circuit layers 7b and 7c are electrically connected to each other via the via hole 11b, and the conductor circuit layers 7b on both surfaces of the substrate are electrically connected to each other via the through hole 3. Next, a solder resist layer 13 is formed on each interlayer insulating layer 8b and the second conductor circuit layer 7c using the composition of the present invention, and a solder bump 14 is formed on the upper solder resist layer 13 (FIG. 5C). Also, the surface of the conductor circuit layer 7c exposed from the lower opening 9b can be plated to obtain a multilayer wiring board as a connection terminal.

  Hereinafter, the present invention will be described in detail with reference to examples and comparative examples of the present invention. However, the present invention is not limited to the following examples. In the following description, “parts” and “%” are all based on mass unless otherwise specified.

<Preparation of thermosetting resin composition>
The components shown in Tables 1 to 5 below are blended, stirred, and kneaded and dispersed in a three-roll mill, and the liquid resin compositions of Examples 1-3, Reference Examples 1-5, and Comparative Examples 1-7. Viscosity for compositions for the dry film of Examples 4 to 8, Reference Examples 6 to 14 and Comparative Examples 8 to 12 with a viscosity of 250 to 600 dPa · s (rotational viscometer 5 rpm, 25 ° C.). It adjusted so that it might become 0.5-20 dPa * s.

<Production of dry film>
Using the bar coater, the film thickness after drying of the compositions of Examples 4 to 8, Reference Examples 6 to 14 and Comparative Examples 8 to 12 obtained above was described in Tables 6 to 8 and 10 below. It was applied onto a carrier film (PET film; Lumirror 38R75 manufactured by Toray Industries, Inc., thickness 38 μm). Then, it dries for 5 to 10 minutes at 70 to 120 ° C. (average 100 ° C.) in a hot air circulating drying furnace so that the remaining content of the organic solvent after drying becomes the amount shown in Tables 6 to 8 and 10 below. A dry coating film having a resin layer on the carrier film was obtained. Next, the protective film was laminated on the resin layer with a roll laminator at a temperature of 70 ° C., and dry films of Examples and Comparative Examples in which both surfaces were sandwiched with films were obtained.

<Measurement of residual content (%) of organic solvent in dry film>
After peeling the carrier film and the protective film from the dry film of each example and comparative example, about 1.2 g of the resin layer was sampled and put in a container with a tight stopper to accurately determine the mass (W) of the sampled resin layer. Weighed. One drop of ethyl 3-ethoxypropionate as an internal standard substance was added to the container with a pipette, and the mass (We) was accurately weighed. Thereafter, 5 ml of acetone was added with a whole pipette and sealed, and the container was shaken sufficiently to dissolve the collected resin layer. Subsequently, this liquid is filtered with a filter having an opening of 0.5 μm, and the composition of the filtrate is analyzed by gas chromatography (TRACEGULTRA manufactured by Thermo Fisher Scientific Co., Ltd.). From a separately prepared calibration curve, 1 g of the internal standard substance is analyzed. The mass (Ws) of the organic solvent was determined. From these, the residual content of the organic solvent was calculated according to the following formula.
Residual content of organic solvent (% by mass) = (We × Ws / W) × 100

  The measurement conditions in gas chromatography are as follows. Column: Agilent Technologies capillary column DB-1MS (30 m × 0.25 mm), detector: MS (ITQ900), carrier gas: helium, injector temperature: 300 ° C., detector temperature: 230 ° C., column temperature condition: initial temperature 50 After the sample injection, hold at 50 ° C. for 2 minutes, raise the temperature to 10 ° C./300° C., hold for 10 minutes after reaching 300 ° C.

<Flexibility of dry film (bending test)>
In accordance with JIS K5600-5-1 (ISO 1519), by using a cylindrical mandrel bending tester manufactured by BYK-Gardner, the mandrel begins to crack and peel off from the carrier film of each example and comparative example. The softness of the dry film was evaluated from the minimum diameter. The evaluation criteria are as follows. When the flexibility of the dry film is good, the flexibility of the resin layer is high and cracking and powder falling can be suppressed.
A: The diameter was φ2 mm or less, and there was no occurrence of cracking of the resin layer, powder falling, or peeling of the carrier film.
○: In the range of more than φ2 mm and less than 5 mm, there was no occurrence of cracking of the resin layer, powder falling, or peeling of the carrier film.
Δ: In the range of more than φ2 mm and less than 5 mm, cracking of the resin layer, powder falling, and peeling of the carrier film occurred.
X: Cracking of resin layer, powder falling, and peeling of carrier film occurred at a diameter of φ5 mm or more.

<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 on the glossy surface side (copper foil) of GTS-MP foil (manufactured by Furukawa Circuit Foil Co., Ltd.) with an applicator, and at 150 ° C. in a hot air circulating drying oven. Cured for 60 minutes.

(Preparation of dry film evaluation sample)
The dry film of each Example and Comparative Example was peeled off the protective film, and the batch type vacuum pressure laminator MVLP-500 on the glossy surface side (copper foil) of GTS-MP foil (Furukawa Circuit Foil Co., Ltd.). (Made by Meiki Co., Ltd.) was used for lamination. Lamination was carried out under the conditions of 5 kgf / cm ² , 80 ° C., 1 minute, 1 Torr, and then leveled with a hot plate press at 10 kgf / cm ² , 80 ° C., 1 minute. Next, the resin layer was cured at 180 ° C. for 60 minutes in a hot air circulation type drying furnace. Moreover, regarding the composition containing the maleimide compound described in Example 6 and Reference Example 12, the resin layer was cured at 220 ° C. for 60 minutes.

(Measurement of glass transition temperature (Tg) and thermal expansion coefficient (CTE (α1)))
Then, after peeling off the hardened | cured material produced by the said method from copper foil, the sample was cut out to measurement size (size of 3 mm x 10 mm), and it used for TMA6100 by Seiko Instruments Inc. In the TMA measurement, the test weight was 5 g, and the sample was heated from room temperature at a heating rate of 10 ° C./min, and was measured twice continuously. The intersection of two tangents having different thermal expansion coefficients in the second round was defined as the glass transition temperature (Tg), and the thermal expansion coefficient (CTE (α1)) in the region below Tg was evaluated. It can be said that the higher the Tg, the higher the heat resistance.
[Evaluation criteria for glass transition temperature (Tg)]
A: Tg is 190 ° C. or higher.
(Double-circle): Tg is 160 degreeC or more and less than 190 degreeC.
A: Tg is 150 ° C. or higher and lower than 160 ° C.
X: Tg is less than 150 degreeC.
[Evaluation Criteria for Thermal Expansion Coefficient (CTE (α1))]
A: Less than 20 ppm.
○: 20 ppm to less than 35 ppm.

<Filling through hole>
(Preparation of evaluation sample of liquid composition)
The liquid resin composition of each Example and Comparative Example was screen 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 a through hole in which a conductor layer was formed by panel plating. Thus, the through holes were filled under the following printing conditions. After filling, it was placed in a hot air circulation drying oven and cured at 150 ° C. for 60 minutes to obtain an evaluation substrate. Fillability was evaluated by the degree of filling of the cured product filled in the through holes of the evaluation substrate.

<Printing conditions>
Squeegee: Squeegee thickness 20mm, hardness 70 °, oblique polishing: 23 °,
Plate: PET100 mesh bias plate,
Printing pressure: 50 kg, squeegee speed 30 mm / Sec,
Squeegee angle: 80 °.

(Preparation of dry film evaluation sample)
The dry film of each example and comparative example was peeled off the protective film, and the same glass epoxy as in the above-mentioned “Preparation of evaluation sample of liquid composition” using a batch type vacuum pressure laminator MVLP-500 (manufactured by Meiki Co., Ltd.). A dry film is laminated on both sides of the substrate in the same manner as described in <Glass transition temperature (Tg) and coefficient of thermal expansion (CTE (α1))> on the substrate, and the resin composition is placed in the through hole. Filled. Next, the resin layer was cured in a hot air circulation type drying furnace.

(Evaluation of fillability)
Thereafter, a cross section passing through the center of the through hole in the substrate was cut and polished with a precision cutting machine, and observed with an optical microscope in a cross-sectional state. Evaluation criteria were evaluated according to the following. The number of observation through holes was 200.
A: All through holes are completely filled with resin.
○: 1 to 2 through-holes not completely filled with resin are generated.
Δ: 3 to 50 through holes not completely filled with resin are generated.
X: 51 or more through holes not completely filled with resin are generated.

<Occurrence of voids>
Generation of voids in the through hole was confirmed using the sample evaluated in the above <fillability in through hole>. Evaluation criteria were evaluated according to the following. The number of observation through holes was 200.
A: No generation of voids.
○: A void is generated in 1 to 2 holes.
Δ: 3 to 50 voids are generated.
X: 51 or more voids are generated.

<Measurement of water absorption rate>
(Preparation of evaluation sample of liquid composition)
About the liquid resin composition of each Example and the comparative example, application | coating and hardening were performed by the method similar to the method as described in said <Glass transition temperature (Tg) and a thermal expansion coefficient (CTE ((alpha) 1))>.

(Preparation of dry film evaluation sample)
About the dry film of each Example and the comparative example, the resin layer was hardened | cured by the method similar to the method as described in said <glass transition temperature (Tg) and a thermal expansion coefficient (CTE ((alpha) 1))>.

(Measurement of water absorption)
Then, after peeling the cured product from the copper foil, a sample was cut out to a measurement size (50 mm × 50 mm size), dried at 100 ° C. for 2 hours, completely removed of moisture, and massed with a precision balance. Measurement of (W1) was performed. Then, the sample was immersed in distilled water controlled at 23 ° C. ± 2 ° C., and the mass (W2) after 24 hours was measured. The water absorption was determined by (W2-W1) / W1 × 100 (%).
A: Less than 0.3%.
A: 0.3% or more and less than 0.7%.
○: 0.7% or more and less than 1.0%.
Δ: 1.0% or more and less than 1.4%.
X: 1.4% or more.

<Cooling cycle (suppression of cracks)>
(Preparation of evaluation sample of liquid composition)
The liquid resin compositions of Examples and Comparative Examples were filled into the through holes by the same method as described in the above <Filling properties to through holes>. Then, it heated at 150 degreeC for 60 minute (s) with the hot-air circulation type drying furnace, the resin layer was hardened, and the part of resin which protruded from the board | substrate surface was removed by buffing. Subsequently, processing was carried out in the order of commercially available wet permanganate desmear (manufactured by ATOTECH), electroless copper plating (Sulcup PEA, manufactured by Uemura Kogyo Co., Ltd.), and electrolytic copper plating treatment to obtain an evaluation board with lid plating specifications.

(Preparation of dry film evaluation sample)
About the dry film of each Example and Comparative Example, using a batch-type vacuum pressurization laminator MVLP-500 (manufactured by Meiki Co., Ltd.), in the same manner as the method described in <Filling property to through hole>, A dry film was laminated from both sides of the substrate, and the resin composition was filled into the through holes. Thereafter, the carrier film was peeled off, and heated at 180 ° C. for 30 minutes in a hot air circulating drying furnace to cure the resin layer. Moreover, regarding the composition containing the maleimide compound described in Example 6 and Reference Example 12, the resin layer was cured at 220 ° C. for 60 minutes. Thereafter, vias were formed using a CO ₂ laser processing machine (manufactured by Hitachi Via Mechanics) so that the top diameter was 65 μm and the bottom diameter was 50 μm.

  Next, processing is performed in the order of commercially available wet permanganate desmear (manufactured by ATOTECH), electroless copper plating (Sulcup PEA, manufactured by Uemura Kogyo Co., Ltd.), and electrolytic copper plating treatment, and a copper thickness of 25 μm is formed on the resin layer. Copper plating treatment was performed so as to fill. Next, curing was performed at 190 ° C. for 60 minutes in a hot-air circulating drying oven to obtain a completely cured copper-plated test substrate.

(Cooling cycle implementation)
About the test board | substrate of each Example and comparative example obtained by said method, heat history of 2000 and 2500 cycles was added for 30 minutes at -65 degreeC and 30 minutes at 150 degreeC as 1 cycle.

(Check for cracks in through holes)
The cross-sectional state at the center of the through hole was observed with an optical microscope in the same manner as described in <Filling property to through hole>. Evaluation criteria were evaluated according to the following. The number of observation through holes was 200.
(Double-circle): A crack does not generate | occur | produce in 2000 cycles and 2500 cycles.
○: No cracks occurred in 2000 cycles. 1-5 cracks occurred in 2500 cycles.
X: Cracks occurred at 2000 cycles.

(Check for via cracks)
In order to observe the state of the via bottom and the wall surface with an optical microscope, the central portion of the via was cut and polished with a precision cutting machine, and the cross-sectional state was observed. Evaluation criteria were evaluated according to the following. The number of observation vias was 100 holes.
(Double-circle): A crack does not generate | occur | produce in 2000 cycles and 2500 cycles.
○: No cracks occurred in 2000 cycles. 1-5 cracks occurred in 2500 cycles.
X: Cracks occurred at 2000 cycles.

<Abrasiveness>
(Preparation of evaluation sample of liquid composition)
The liquid resin compositions of the examples and comparative examples were filled into the through holes in the same manner as described in <Filling properties to through holes> above. After filling, it was placed in a hot air circulation drying oven and cured at 150 ° C. for 60 minutes to obtain an evaluation substrate.

(Preparation of dry film evaluation sample)
Using the batch-type vacuum pressurization laminator MVLP-500 (manufactured by Meiki Co., Ltd.), the dry film of each example and comparative example was the same as the method described in the above <Filling through hole>. A dry film was laminated from only one side of the substrate, and then the resin layer was cured.

(Evaluation of abrasiveness)
The portion of the resin protruding from the substrate surface of each of the examples and non-comparative test substrates obtained by the above method is physically polished by buffing, and the number of passes until the resin in the discharge portion is removed is determined. Compared.
A: Polishing is possible in 2 passes or less.
○: Polishing is possible in 2 to 3 passes.
X: 4 passes or more.

<Evaluation of storage stability>
(Evaluation of storage stability of liquid composition)
For each of the liquid resin compositions of Examples 1 to 3, Reference Examples 1 to 5, and Comparative Examples 1 to 7, the viscosity after the initial storage at 25 ° C. for 7 days is measured. Asked.
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% Δ: 30% or more and less than 50% ×: 50% or more

(Evaluation of storage stability of dry film)
About the dry films of Examples 4 to 8, Reference Examples 6 to 14 and Comparative Examples 8 to 12, using “Rheo Stress RS6000” manufactured by Thermo Fisher Scientific Co., Ltd. The melt viscosity was measured. The measurement was performed by peeling the carrier film and the protective film from the dry film of each Example and Comparative Example prepared in a size of 30 mm × 30 mm, and then placing the film on a parallel plate having a diameter of 20 mm, starting temperature from 40 ° C. to 150 ° C., The melt viscosity was measured under the conditions of a temperature elevation temperature of 3 ° C./min, vibration of 1 Hz, and strain of 2 deg, the minimum melt viscosity was determined, and the thickening rate was determined by the following formula.
Thickening rate (%) = (minimum melt viscosity after storage at 25 ° C. for 3 days−initial minimum melt viscosity) / initial minimum melt viscosity × 100
A: Less than 30% B: 30% or more and less than 50%

＊１）ＥＰＯＸ−ＭＫ Ｒ７１０：（株）プリンテック製（ビスフェノールＥ型エポキシ樹脂，エポキシ当量１６０〜１８０ｇ／ｅｑ、液状）
＊２）ＪＥＲ８２８：三菱化学（株）製（ビスフェノールＡ型エポキシ樹脂，エポキシ当量１８４〜１９４ｇ／ｅｑ、液状）
＊３）ＪＥＲ８０７：三菱化学（株）製（ビスフェノールＦ型エポキシ樹脂，エポキシ当量１６０〜１７５ｇ／ｅｑ、液状）
＊４）ＤＥＮ４３１：ダウ・ケミカル社製（フェノールノボラック型エポキシ樹脂（多官能エポキシ樹脂））
＊５）ＪＥＲ６３０：三菱化学（株）製（パラアミノフェノール型液状エポキシ樹脂（多官能エポキシ樹脂），エポキシ当量９０〜１０５ｇ／ｅｑ、液状）
＊６）ＥＤ−５０９Ｓ：（株）ＡＤＥＫＡ製（単官能エポキシ樹脂，エポキシ当量２０６ｇ／ｅｑ）
＊７）ＨＰ−４０３２：ＤＩＣ（株）製（ナフタレン型エポキシ樹脂，エポキシ当量１３５〜１６５ｇ／ｅｑ；半固体）
＊８）ＨＰ−７２００Ｌ：ジシクロペンタジエン型エポキシ樹脂（ＤＩＣ社製，エポキシ当量２５０〜２８０ｇ／ｅｑ；軟化点５７〜６８℃）
＊９）ＨＦ−１Ｍ：明和化成社製（フェノールノボラック樹脂）
＊１０）ＳＮ−４８５：新日鉄住金化学（株）製（フェノールノボラック樹脂）
＊１１）ＬＡ−７０５４：ＤＩＣ社製（フェノールノボラック樹脂）
＊１２）ＰＴ−３０：ロンザジャパン社製（フェノールノボラック型多官能シアネート樹脂）
＊１３）ＨＰＣ−８０００：活性エステル樹脂（ＤＩＣ社製）
＊１４）ＢＭＩ−２３００：大和化成工業（株）製
＊１５）ソフトン１８００：備北粉化工業社製、炭酸カルシウムＣａＣＯ_３（平均粒径１．２５μｍ）
＊１６）（株）アドマテックス製、シリカＳｉＯ_２（Ｄ５０＝０．５μｍ）
＊１７）２ＭＺ−ＡＰ：四国化成工業（株）製
＊１８）２Ｅ４ＭＺ
＊１９）ＤＭＡＰ：４−ジメチルアミノピリジン
＊２０）ＦＸ−２９３：新日鉄住金化学（株）製（フェノキシ樹脂）

* 1) EPOX-MK R710: manufactured by Printec Co., Ltd. (bisphenol E type epoxy resin, epoxy equivalent 160-180 g / eq, liquid)
* 2) JER828: manufactured by Mitsubishi Chemical Corporation (bisphenol A type epoxy resin, epoxy equivalent of 184 to 194 g / eq, liquid)
* 3) JER807: manufactured by Mitsubishi Chemical Corporation (bisphenol F type epoxy resin, epoxy equivalent of 160 to 175 g / eq, liquid)
* 4) DEN431: manufactured by Dow Chemical Company (phenol novolac type epoxy resin (polyfunctional epoxy resin))
* 5) JER630: manufactured by Mitsubishi Chemical Corporation (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: manufactured by DIC Corporation (Naphthalene type epoxy resin, epoxy equivalent of 135 to 165 g / eq; semi-solid)
* 8) HP-7200L: dicyclopentadiene type epoxy resin (manufactured by DIC, epoxy equivalent 250-280 g / eq; softening point 57-68 ° C.)
* 9) HF-1M: Meiwa Kasei Co., Ltd. (phenol novolac resin)
* 10) SN-485: manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. (phenol novolac resin)
* 11) LA-7054: manufactured by DIC (phenol novolac resin)
* 12) PT-30: Lonza Japan Co., Ltd. (phenol novolac polyfunctional cyanate resin)
* 13) HPC-8000: Active ester resin (manufactured by DIC)
* 14) BMI-2300: manufactured by Daiwa Kasei Kogyo Co., Ltd. * 15) Softon 1800: manufactured by Bihoku Flour Chemical Co., Ltd., calcium carbonate CaCO ₃ (average particle size: 1.25 μm)
* 16) Silica SiO ₂ (D50 = 0.5 μm), manufactured by Admatechs Co., Ltd.
* 17) 2MZ-AP: Shikoku Kasei Kogyo Co., Ltd. * 18) 2E4MZ
* 19) DMAP: 4-dimethylaminopyridine * 20) FX-293: Nippon Steel & Sumikin Chemical Co., Ltd. (phenoxy resin)

  As shown in the above table, the composition of each example using a bisphenol E type epoxy resin as an epoxy resin has a high Tg and a low CTE, has a low water absorption, fillability to through holes, and TCT resistance. It was confirmed that it was excellent in abrasiveness and could suppress the generation of voids.

  In addition, in Reference Example 2 in which calcium carbonate and silica are used in combination as the filler for the liquid resin composition, CTE is further reduced and TCT resistance is improved as compared with Reference Example 1 using only calcium carbonate. I understand that. (A) In Examples 1 to 3, in which a small amount of bisphenol A type epoxy resin and bisphenol F type epoxy resin was added to bisphenol E type epoxy resin, the storage stability was improved, and an aminophenol type epoxy resin was further added. In Example 3 and Reference Examples 3 to 5, it can be seen that Tg is improved and heat resistance is further improved as compared to Reference Example 1 in which the component (A) is used alone.

  Furthermore, as compared with Reference Example 6 in which (A) bisphenol E type epoxy resin and semi-solid epoxy resin are used in combination as the epoxy resin for the dry film, Reference Example 7 in which a solid epoxy resin is used in combination with (A) component. Then, Tg became higher and the TCT resistance was improved. Furthermore, in Reference Example 8 in which a semisolid epoxy resin and a solid epoxy resin were used together with (A) a bisphenol E type epoxy resin, the flexibility was also excellent. I understand that. In Examples 4 to 8 in which the liquid epoxy resin was changed to the combination of the E type component (A) and the A type and F type components from the formulation of Reference Example 8, the CTE decreased due to the inclusion of the A type. In addition, the storage stability is excellent, and in Reference Example 9 in which the amount of silica is further increased, the CTE is further lowered. Moreover, in Reference Example 10 in which the silica was changed to calcium carbonate from the formulation of Reference Example 8, the abrasiveness was further improved. Furthermore, even in Reference Example 11 in which a colorant is added to the formulation of Reference Example 8, the same performance as in Reference Example 8 is obtained, and in Reference Example 12 in which a bismaleimide resin is added, Tg is further improved. Furthermore, in Reference Examples 13 and 14 in which the curing agent and the curing accelerator are changed from those of Reference Example 8 to those having no hydroxyl group, the water absorption rate is improved.

  On the other hand, as for the liquid resin composition, in Comparative Example 1 in which only the A-type epoxy resin was used, the viscosity increased, the filling property decreased, and the generation of voids was inferior. In Comparative Example 2 using only the mold type, Tg was lowered and TCT resistance was deteriorated. In Comparative Example 3 in which A type and F type were used in combination, the filling property was reduced and the generation of voids was prevented. In terms of the point, Tg is lowered and TCT resistance is deteriorated. Further, in Comparative Example 4 in which only the aminophenol type epoxy resin was used, the water absorption rate was deteriorated, voids were generated, and the abrasiveness was also deteriorated. Comparison using the F type and aminophenol type in combination In Example 5, the water absorption rate deteriorated and voids were generated. In Comparative Example 6 in which the phenol novolac type and aminophenol type were used in combination, the water absorption rate deteriorated and voids were generated. Yes. Furthermore, in Comparative Example 7 in which A type and a monofunctional epoxy resin are used in combination as an epoxy resin, Tg is lowered and TCT resistance is deteriorated.

  Further, as for the dry film, in Comparative Example 8 in which only the A type epoxy resin was used, the flexibility was lowered, and in Comparative Example 9 in which only the F type was used, Tg was lowered and TCT was reduced. In the comparative example 10 in which the A type and the F type are used in combination, the Tg is lowered and the TCT resistance is deteriorated. Further, among Comparative Examples 11 and 12 in which no liquid epoxy resin is blended as an epoxy resin, Comparative Example 11 with a small amount of residual solvent has a reduced flexibility and filling property and has a large amount of residual solvent. In FIG. 12, a void has occurred.

1 Substrate 2 Copper foil 3 Through hole 4 Plating film 5 Resin composition
6 Etching resist 7 Conductor circuit layer 8 Interlayer resin insulation layer 9 Opening 10 Plating resist layer 11 Via hole 12 Land 13 Solder resist layer 14 Solder bump 30a Liquid determination test tube 30b Temperature measurement test tube 31 Mark (A line)
32 Mark (B line)
33a, 33b Rubber plug 34 Thermometer X Laminated substrate 101 Insulating substrate 103 Inner layer conductor pattern 103a Connection portion 104, 109 Resin insulating layer 108 Outer layer conductor pattern 110 Outermost layer conductor pattern 120 Through hole 121 Through hole hole 122 Connection portion

Claims (9)

(A) a bisphenol E type epoxy resin;
(B) either one or both of a curing agent and a curing accelerator,
(C) a non-metallic filler;
Furthermore, the insulating thermosetting resin composition characterized by containing a bisphenol A type epoxy resin and a bisphenol F type epoxy resin, and being used for hole filling. The insulating thermosetting resin composition according to claim 1, which does not contain a solvent. The insulating thermosetting resin composition according to claim 1 or 2, which does not contain a semi-solid epoxy resin and a solid epoxy resin. The insulating thermosetting resin composition according to any one of claims 1 to 3, 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 any one of claims 1 to 4 , wherein the non-metallic filler (C) includes one or both of calcium carbonate and silica. A dry film comprising a resin layer obtained by applying and drying the insulating thermosetting resin composition according to any one of claims 1 to 5 on a film. The dry film according to claim 6, wherein the residual solvent amount of the resin layer is less than 1% by mass based on the total amount of the resin layer containing the solvent. Curing characterized by being obtained by curing the insulating thermosetting resin composition according to any one of claims 1 to 5 , or the resin layer of the dry film according to claim 6 or 7. object. A printed wiring board comprising the cured product according to claim 8 .

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