JP6317069B2 - Printed wiring board material and printed wiring board using the same - Google Patents

Description

  The present invention relates to a printed wiring board material and a printed wiring board using the same.

  As a wiring board such as a printed wiring board, a metal material such as copper is applied to a fiber such as glass impregnated with an epoxy resin, which is called a core material, and a circuit is formed by an etching method, There is one in which a circuit is formed after an insulating layer is formed by coating an insulating resin composition or laminating a sheet-like insulating resin composition. As a method for producing a multilayer printed wiring board, there is conventionally known a method of laminating and pressing a plurality of circuit boards formed with circuits through a prepreg as an adhesive insulating layer and connecting each layer circuit by through holes. Yes. On the other hand, in recent years, as a manufacturing method of a multilayer printed wiring board, a build-up manufacturing technology in which an interlayer insulating material and a conductor layer are alternately stacked on a conductor layer of an inner circuit board has been attracting attention (for example, (See Patent Documents 1 and 2).

  In addition, a solder resist is formed on the outermost layer of the wiring board for the purpose of protecting the formed circuit and mounting the electronic component at the correct position. In general, an insulating material such as an epoxy resin or an acrylate resin is used for the solder resist (see, for example, Patent Document 3).

  Various properties are required for materials applied to such printed wiring boards, and a low coefficient of linear expansion is one of the important required characteristics.

JP 2006-182991 A (Claims etc.) JP 2013-36042 A (Claims etc.) Japanese Patent Laid-Open No. 08-269172 (Claims etc.)

  The objective of this invention is providing the printed wiring board material which can implement | achieve a low linear expansion coefficient compared with the past, and a printed wiring board using the same.

  As a result of intensive studies, the present inventors have formulated a combination of cellulose nanofibers and layered silicates into a printed wiring board material, so that the linear expansion coefficient is smaller than when either one is blended. As a result, the present invention has been completed.

  That is, the printed wiring board material of the present invention includes a binder component, cellulose nanofibers having a number average fiber diameter of 3 nm to 1000 nm, and a layered silicate.

  In the printed wiring board material of the present invention, a thermoplastic resin and a curable resin can be suitably used as the binder component. The printed wiring board material of the present invention can be suitably used for solder resists, core materials, and interlayer insulating materials for multilayer printed wiring boards.

  The printed wiring board of the present invention is characterized by using the printed wiring board material of the present invention.

  According to the present invention, the above configuration makes it possible to realize a printed wiring board material capable of realizing a lower linear expansion coefficient than the conventional one and a printed wiring board using the same.

It is a fragmentary sectional view which shows one structural example of the multilayer printed wiring board which concerns on this invention.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.
The printed wiring board material of the present invention is characterized in that it includes a binder component, cellulose nanofibers having a number average fiber diameter of 3 nm to 1000 nm, and a layered silicate.

The cellulose nanofiber can be obtained as follows.
As raw materials for cellulose nanofibers, use pulp made from natural plant fiber materials such as wood, hemp, bamboo, cotton, jute, kenaf, beet, agricultural waste, cloth, regenerated cellulose fibers such as rayon and cellophane, etc. Among them, pulp is particularly preferable. As pulp, chemical pulp such as kraft pulp and sulfite pulp, semi-chemical pulp, chemi-ground pulp, chemimechanical pulp, obtained by pulping plant raw materials chemically or mechanically, or a combination of both, Thermomechanical pulp, chemithermomechanical pulp, refiner mechanical pulp, groundwood pulp, deinked wastepaper pulp, magazine wastepaper pulp, corrugated wastepaper pulp and the like mainly composed of these plant fibers can be used. Among them, various kraft pulps derived from conifers having strong fiber strength, for example, softwood unbleached kraft pulp, softwood oxygen bleached unbleached kraft pulp, and softwood bleached kraft pulp are particularly suitable.

  The raw material is mainly composed of cellulose, hemicellulose, and lignin, and the content of lignin is usually about 0 to 40% by mass, particularly about 0 to 10% by mass. About these raw materials, the removal of a lignin thru | or a bleaching process can be performed as needed, and the amount of lignin can be adjusted. The lignin content can be measured by the Klason method.

  In the cell wall of a plant, cellulose molecules are not a single molecule but regularly agglomerate to form crystalline microfibrils (cellulose nanofibers) that gather together and form the basic skeletal material of plants. ing. Therefore, in order to produce cellulose nanofibers from the above raw materials, a method of unraveling the fibers to the nano size by subjecting the raw materials to beating or crushing treatment, high-temperature high-pressure steam treatment, treatment with phosphate, etc. Can be used.

  Among the above, the beating or pulverization treatment is a method of obtaining cellulose nanofibers by applying a force directly to the raw materials such as pulp, mechanically beating or pulverizing, and unraveling the fibers. More specifically, for example, pulp fibers and the like are mechanically treated with a high-pressure homogenizer or the like, and the cellulose fibers that have been loosened to a fiber diameter of about 0.1 to 10 μm are made into an aqueous suspension of about 0.1 to 3% by mass. Furthermore, cellulose nanofibers having a fiber diameter of about 10 to 100 nm can be obtained by repeatedly grinding or crushing them with a grinder or the like.

  The grinding or crushing treatment can be performed using, for example, a grinder “Pure Fine Mill” manufactured by Kurita Machine Seisakusho. This grinder is a stone mill that pulverizes raw materials into ultrafine particles by impact, centrifugal force and shearing force generated when the raw material passes through the gap between the upper and lower two grinders. Shearing, grinding, atomization Dispersion, emulsification and fibrillation can be performed simultaneously. Further, the above grinding or crushing treatment can also be carried out using an ultrafine grinding machine “Supermass colloider” manufactured by Masuko Sangyo Co., Ltd. The Super Mass Collider is an attritor that enables ultra-fine atomization that feels like melting beyond the mere grinding area. The super mass collider is a stone mill type ultrafine grinding machine composed of two top and bottom non-porous grindstones whose spacing can be freely adjusted. The upper grindstone is fixed and the lower grindstone rotates at high speed. The raw material thrown into the hopper is fed into the gap between the upper and lower grinding stones by centrifugal force, and the raw material is gradually crushed by the strong compression, shearing, rolling frictional force, etc. generated there, and is made into ultrafine particles.

  The high-temperature and high-pressure steam treatment is a method for obtaining cellulose nanofibers by unraveling the fibers by exposing raw materials such as pulp to high-temperature and high-pressure steam.

  Furthermore, the treatment with the phosphate or the like is performed by phosphatizing the surface of the raw material such as the pulp to weaken the bonding force between the cellulose fibers, and then performing refiner treatment to unravel the fibers, This is a processing method for obtaining nanofibers. For example, the raw materials such as pulp are immersed in a solution containing 50% by mass of urea and 32% by mass of phosphoric acid, and the solution is sufficiently soaked between cellulose fibers at 60 ° C., and then heated at 180 ° C. After proceeding with phosphorylation and washing with water, it was hydrolyzed in a 3% by mass aqueous hydrochloric acid solution at 60 ° C. for 2 hours, washed again with water, and then further washed with a 3% by mass aqueous sodium carbonate solution. Cellulose nanofibers can be obtained by completing phosphorylation by treating at room temperature for about 20 minutes and defibrating the treated product with a refiner.

  In addition, the cellulose nanofiber used in the present invention may be chemically modified and / or physically modified to enhance functionality. Here, as the chemical modification, a functional group is added by acetalization, acetylation, cyanoethylation, etherification, isocyanateation, etc., or inorganic substances such as silicate and titanate are combined by chemical reaction or sol-gel method, Or it can carry out by the method of coat | covering. Examples of the chemical modification method include a method in which cellulose nanofibers formed into a sheet are immersed in acetic anhydride and heated. Examples of the physical modification method include physical vapor deposition (PVD method) such as vacuum deposition, ion plating, sputtering, chemical vapor deposition (CVD), electroless plating, electrolytic plating, etc. The method of covering by the plating method etc. of this is mentioned. These modifications may be before the treatment or after the treatment.

  The number average fiber diameter of the cellulose nanofiber used in the present invention is required to be 3 nm to 1000 nm, preferably 3 nm to 200 nm, and more preferably 3 nm to 100 nm. Since the minimum diameter of the cellulose nanofiber single fiber is 3 nm, it is not possible to produce substantially less than 3 nm, and when it exceeds 1000 nm, it is necessary to add excessively in order to obtain the desired effect of the present invention. The film forming property is deteriorated. In addition, the number average fiber diameter of the cellulose nanofiber is observed with SEM (Scanning Electron Microscope; Scanning Electron Microscope), TEM (Transmission Electron Microscope; Transmission Electron Microscope), etc., and the diagonal line of the photograph is drawn. This is an average value obtained by extracting 12 points of fibers in the vicinity at random, removing the thickest fiber and the thinnest fiber, and measuring the remaining 10 points.

  The blending amount of the cellulose nanofiber used in the present invention is preferably 0.04 to 64% by mass, more preferably 0.08 to 56% by mass, based on the total amount of the composition excluding the solvent. When the blending amount of the cellulose nanofiber is 0.04% by mass or more, the effect of reducing the linear expansion coefficient can be favorably obtained. On the other hand, in the case of 64 mass% or less, film forming property improves.

  The layered silicate is not particularly limited, but clay minerals and hydrotalcite compounds having swelling properties and / or cleavage properties, and similar compounds are preferable. Examples of these clay minerals include kaolinite, dickite, nacrite, halloysite, antigolite, chrysotile, pyrophyllite, montmorillonite, beidellite, nontronite, saponite, sauconite, stevensite, hectorite, tetrasilic mica, sodium. Examples include teniolite, muscovite, margarite, talc, vermiculite, phlogopite, xanthophyllite, chlorite. These layered silicates may be natural products or synthetic products. These layered silicates can be used alone or in combination.

  The shape of the layered silicate is not particularly limited, but it is difficult to cleave after layering when the layered silicate overlaps multiple layers. The thickness of the salt is preferably as thick as possible in one layer (about 1 nm). Further, those having an average length of 0.01 to 50 μm, preferably 0.05 to 10 μm, and an aspect ratio of 20 to 500, preferably 50 to 200 can be suitably used.

  The layered silicate has an inorganic cation capable of ion exchange between the layers. The ion-exchangeable inorganic cation is a metal ion such as sodium, potassium, or lithium existing on the surface of the layered silicate crystal. These ions have an ion exchange property with a cationic substance, and various substances having a cationic property can be inserted (intercalated) between the layers of the layered silicate by an ion exchange reaction.

  The cation exchange capacity (CEC) of the layered silicate is not particularly limited, but is preferably, for example, 25 to 200 meq / 100 g, more preferably 50 to 150 meq / 100 g, and 90 to 130 meq. More preferably, it is / 100g. If the cation exchange capacity of the layered silicate is 25 meq / 100 g or more, a sufficient amount of a cationic substance is inserted (intercalated) between the layers of the layered silicate by ion exchange, and the layers are sufficiently made organophilic. . On the other hand, if the cation exchange capacity is 200 meq / 100 g or less, the bonding strength between the layers of the layered silicate becomes too strong and the crystal flakes are not easily peeled off, and good dispersibility can be maintained.

  Specific examples of the layered silicate satisfying the above preferred conditions include, for example, Sumecton SA manufactured by Kunimine Industry Co., Ltd., Kunipia F manufactured by Kunimine Industry Co., Ltd., Somasif ME-100 manufactured by Corp Chemical Co., Ltd. Examples of such products include Lucentite STN manufactured by Chemical Corporation.

  In addition, as a layered silicate organic agent used in the present invention, any general onium salt may be used. From the viewpoint of heat resistance, it is disclosed in JP-A-2004-107541. It is preferable to use an onium salt having a high thermal decomposition temperature.

  The method for containing the organophilic agent between the layered silicate layers is not particularly limited, but from the viewpoint that the synthesis operation is easy, the inorganic cation is made to be an organophilic agent by an ion exchange reaction. A method of containing them by exchanging them with each other is preferable. The method for ion-exchanging the ion-exchangeable inorganic cation of the layered silicate with the organophilic agent is not particularly limited, and a known method can be used. Specifically, techniques such as ion exchange in water, ion exchange in alcohol, and ion exchange in a water / alcohol mixed solvent can be used.

  Specifically, after sufficiently solvating the layered silicate with water, alcohol or the like, an organophilic agent is added and stirred to replace the inorganic cation between the layers of the layered silicate with the organophilic agent. Thereafter, the unsubstituted organophilic agent is thoroughly washed, filtered and dried. In addition, it is also possible to react the layered silicate and organic cation directly in an organic solvent, or to react the layered silicate and the organophilic agent in the presence of a resin while heating and kneading them in an extruder. is there.

  The progress of the ion exchange can be confirmed by a known method. For example, the method of confirming the exchanged inorganic ions by ICP emission analysis of the filtrate, the method of confirming that the layer spacing of the layered silicate has been expanded by X-ray analysis, It can be confirmed that the inorganic cation of the layered silicate has been replaced with the organophilic agent by a method for confirming the presence of the organic agent. The ion exchange is preferably 0.05 equivalents (5% by mass) or more, more preferably 0.1 equivalents (10% by mass) or more with respect to 1 equivalent of inorganic ions capable of ion exchange of the layered silicate. Preferably, it is 0.5 equivalent (50 mass%) or more. The ion exchange is preferably performed at a temperature of 0 to 100 ° C, more preferably at a temperature range of 10 to 90 ° C, and further preferably at a temperature range of 15 to 80 ° C.

  Moreover, the compounding quantity of the said layered silicate used for this invention is 0.02-48 mass% suitably with respect to the whole quantity of the composition except a solvent, More preferably, it is 0.04-42 mass%. is there. When the compounding quantity of layered silicate is 0.02 mass% or more, the reduction effect of a linear expansion coefficient can be acquired favorably. On the other hand, in the case of 48 mass% or less, film forming property improves.

  According to the present invention, by combining cellulose nanofibers and layered silicates, a material having a greatly reduced linear expansion coefficient with a smaller amount than when either one is blended due to a synergistic effect. Can be obtained. The total amount of the cellulose nanofiber and the layered silicate in the present invention is preferably 0.1 to 80% by mass, more preferably 0.2 to 70% by mass with respect to the total amount of the composition excluding the solvent. %.

  As the binder component used in the present invention, a thermoplastic resin and a curable resin such as a thermosetting resin or a photocurable resin can be suitably used.

(Thermoplastic resin)
Thermoplastic resins include acrylic, modified acrylic, low density polyethylene, high density polyethylene, ethylene-vinyl acetate copolymer, polyethylene terephthalate, polypropylene, modified polypropylene, polystyrene, acrylonitrile-butadiene-styrene copolymer, acrylonitrile-styrene copolymer. General-purpose plastics such as polymers, cellulose acetate, polyvinyl alcohol, polyvinyl chloride, polyvinylidene chloride, polylactic acid, polyamide, thermoplastic polyurethane, polyacetal, polycarbonate, ultrahigh molecular weight polyethylene, polybutylene terephthalate, modified polyphenylene ether, polysulfone, Polyphenylene sulfide, polyethersulfone, polyetheretherketone, polyarylate, polyetherimide, polyar Doimide, liquid crystal polymer, polyamide 6T, polyamide 9T, polytetrafluoroethylene, polyvinylidene fluoride, polyesterimide, engineering plastics such as thermoplastic polyimide, olefin, styrene, polyester, urethane, amide, vinyl chloride And thermoplastic elastomers such as hydrogenated systems.

(Thermosetting resin)
The thermosetting resin may be any resin that is cured by heating and exhibits electrical insulation. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol E type epoxy resin, bisphenol M type epoxy resin, bisphenol P type epoxy resin, bisphenol type epoxy resin such as bisphenol Z type epoxy resin, bisphenol A novolac type epoxy resin, phenol novolac type epoxy resin, novolac type epoxy resin such as cresol novolac epoxy resin, biphenyl type epoxy Resin, biphenyl aralkyl type epoxy resin, aryl alkylene type epoxy resin, tetraphenylol ethane type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin Fatty, phenoxy type epoxy resin, dicyclopentadiene type epoxy resin, norbornene type epoxy resin, adamantane type epoxy resin, fluorene type epoxy resin, glycidyl methacrylate copolymer epoxy resin, copolymer epoxy resin of cyclohexylmaleimide and glycidyl methacrylate , Epoxy-modified polybutadiene rubber derivatives, CTBN-modified epoxy resins, trimethylolpropane polyglycidyl ether, phenyl-1,3-diglycidyl ether, biphenyl-4,4′-diglycidyl ether, 1,6-hexanediol diglycidyl ether , Ethylene glycol or propylene glycol diglycidyl ether, sorbitol polyglycidyl ether, tris (2,3-epoxypropyl) isocyanurate Modified with novolak type phenolic resin such as triglycidyl tris (2-hydroxyethyl) isocyanurate, phenol novolak resin, cresol novolak resin, bisphenol A novolak resin, unmodified resole phenolic resin, tung oil, linseed oil, walnut oil, etc. Phenol resins such as resol type phenol resins such as oil-modified resole phenol resin, triazine ring-containing resins such as phenoxy resin, urea (urea) resin, melamine resin, unsaturated polyester resin, bismaleimide resin, diallyl phthalate resin, silicone resin, Resin having benzoxazine ring, norbornene resin, cyanate resin, isocyanate resin, urethane resin, benzocyclobutene resin, maleimide resin, bismaleimide triazine resin, polyester Azomethine resins, thermosetting polyimides.

(Photo-curing resin (radical polymerization))
Such a photocurable resin may be any resin that is cured by irradiation with active energy rays and exhibits electrical insulation, and particularly a compound having one or more ethylenically unsaturated bonds in the molecule is preferably used. As the compound having an ethylenically unsaturated bond, known and commonly used photopolymerizable oligomers and photopolymerizable vinyl monomers are used.

  Examples of the photopolymerizable oligomer include unsaturated polyester oligomers and (meth) acrylate oligomers. Examples of (meth) acrylate oligomers include phenol novolac epoxy (meth) acrylate, cresol novolac epoxy (meth) acrylate, epoxy (meth) acrylates such as bisphenol type epoxy (meth) acrylate, urethane (meth) acrylate, epoxy urethane (meta ) Acrylate, polyester (meth) acrylate, polyether (meth) acrylate, polybutadiene-modified (meth) acrylate, and the like. 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.

  As the photopolymerizable vinyl monomer, known and commonly used monomers, for example, styrene derivatives such as styrene, chlorostyrene and α-methylstyrene; vinyl esters such as vinyl acetate, vinyl butyrate or vinyl benzoate; vinyl isobutyl ether, vinyl- vinyl ethers such as n-butyl ether, vinyl-t-butyl ether, vinyl-n-amyl ether, vinyl isoamyl ether, vinyl-n-octadecyl ether, vinyl cyclohexyl ether, ethylene glycol monobutyl vinyl ether, triethylene glycol monomethyl vinyl ether; acrylamide, Methacrylamide, N-hydroxymethylacrylamide, N-hydroxymethylmethacrylamide, N-methoxymethylacrylamide, N-ethoxymethylacrylate (Meth) acrylamides such as luamide and N-butoxymethylacrylamide; allyl compounds such as triallyl isocyanurate, diallyl phthalate and diallyl isophthalate; 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, tetrahydrofurfuryl Esters of (meth) acrylic acid such as (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate, phenoxyethyl (meth) acrylate; hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, pentaerythritol Hydroxyalkyl (meth) acrylates such as tri (meth) acrylate; alcohols such as methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate Xylalkylene glycol mono (meth) acrylates; ethylene glycol di (meth) acrylate, butanediol di (meth) acrylates, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylol Alkylene polyol poly (meth) acrylates such as propane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, Polyoxyalkylene glycol poly (such as ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane tri (meth) acrylate) A) acrylates; poly (meth) acrylates such as neopentyl glycol ester di (meth) acrylate of hydroxybivalic acid; isocyanurate type poly (meth) acrylates such as tris [(meth) acryloxyethyl] isocyanurate Is mentioned.

(Photocurable resin (cationic polymerization))
As such a photocurable resin, an alicyclic epoxy compound, an oxetane compound, a vinyl ether compound and the like can be suitably used. Among these, alicyclic epoxy compounds include 3,4,3 ′, 4′-diepoxybicyclohexyl, 2,2-bis (3,4-epoxycyclohexyl) propane, and 2,2-bis (3,4-epoxy). Cyclohexyl) -1,3-hexafluoropropane, bis (3,4-epoxycyclohexyl) methane, 1- [1,1-bis (3,4-epoxycyclohexyl)] ethylbenzene, bis (3,4-epoxycyclohexyl) Adipate, 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate, (3,4-epoxy-6-methylcyclohexyl) methyl-3 ′, 4′-epoxy-6-methylcyclohexanecarboxylate, ethylene -1,2-bis (3,4-epoxycyclohexanecarboxylic acid) ester, chic Examples thereof include alicyclic epoxy compounds having an epoxy group such as rohexene oxide, 3,4-epoxycyclohexylmethyl alcohol, and 3,4-epoxycyclohexylethyltrimethoxysilane. Examples of commercially available products include Celoxide 2000, Celoxide 2021, Celoxide 3000, and EHPE3150 manufactured by Daicel Chemical Industries, Ltd .; Epomic VG-3101 manufactured by Mitsui Chemicals, Inc .; E-1031S manufactured by Yuka Shell Epoxy Co., Ltd. ; TETRAD-X, TETRAD-C manufactured by Mitsubishi Gas Chemical Co., Ltd .; EPB-13, EPB-27 manufactured by Nippon Soda Co., Ltd., and the like.

  Examples of the oxetane compound include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether, 1,4-bis [(3-methyl-3- Oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3-methyl-3-oxetanyl) methyl acrylate, (3-ethyl-3-oxetanyl) methyl acrylate In addition to polyfunctional oxetanes such as (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate and oligomers or copolymers thereof, oxetane alcohol and novolak resin, poly (p -Hydroxystyrene), cardo-type bisphenols Examples include oxetane compounds such as calixarenes, calixresorcinarenes, etherification products with hydroxyl group-containing resins such as silsesquioxane, and copolymers of unsaturated monomers having an oxetane ring and alkyl (meth) acrylates. . Commercially available products include, for example, Etanacol OXBP, OXMA, OXBP, EHO, xylylene bisoxetane manufactured by Ube Industries, Ltd., Aron Oxetane OXT-101, OXT-201, XT-211, OXT manufactured by Toagosei Co., Ltd. -221, OXT-212, OXT-610, PNOX-1009, and the like.

  Examples of vinyl ether compounds include cyclic ether type vinyl ethers such as isosorbite divinyl ether and oxanorbornene divinyl ether (vinyl ethers having cyclic ether groups such as oxirane ring, oxetane ring and oxolane ring); aryl vinyl ethers such as phenyl vinyl ether; n-butyl vinyl ether Alkyl vinyl ethers such as octyl vinyl ether; cycloalkyl vinyl ethers such as cyclohexyl vinyl ether; polyfunctional vinyl ethers such as hydroquinone divinyl ether, 1,4-butanediol divinyl ether, cyclohexane divinyl ether, cyclohexane dimethanol divinyl ether, α and / or β position And vinyl ether compounds having substituents such as alkyl groups and allyl groups. The Examples of commercially available products include 2-hydroxyethyl vinyl ether (HEVE), diethylene glycol monovinyl ether (DEGV), 2-hydroxybutyl vinyl ether (HBVE), and triethylene glycol divinyl ether manufactured by Maruzen Petrochemical Co., Ltd.

  When the printed wiring board material of the present invention is used as an alkali development type photo solder resist that can be developed with an aqueous alkali solution, it is also preferable to use a carboxyl group-containing resin as a binder component.

(Carboxyl group-containing resin)
As the carboxyl group-containing resin, any of a photosensitive carboxyl group-containing resin having at least one photosensitive unsaturated double bond and a carboxyl group-containing resin having no photosensitive unsaturated double bond can be used. However, it is not limited to a specific one. As the carboxyl group-containing resin, in particular, the resins listed below can be suitably used.
(1) A carboxyl group-containing resin obtained by copolymerization of an unsaturated carboxylic acid and a compound having an unsaturated double bond, and a carboxyl group-containing resin having a molecular weight and an acid value adjusted by modifying it.
(2) A photosensitive carboxyl group-containing resin obtained by reacting a carboxyl group-containing (meth) acrylic copolymer resin with a compound having an oxirane ring and an ethylenically unsaturated group in one molecule.
(3) An unsaturated monocarboxylic acid is reacted with a copolymer of a compound having one epoxy group and an unsaturated double bond in each molecule and a compound having an unsaturated double bond, and formed by this reaction. A photosensitive carboxyl group-containing resin obtained by reacting a secondary hydroxyl group with a saturated or unsaturated polybasic acid anhydride.
(4) After reacting a hydroxyl group-containing polymer with a saturated or unsaturated polybasic acid anhydride, a compound having one epoxy group and an unsaturated double bond in each molecule of the carboxylic acid produced by this reaction. Photosensitive hydroxyl group and carboxyl group-containing resin obtained by reaction.
(5) A photosensitive carboxyl group obtained by reacting a polyfunctional epoxy compound with an unsaturated monocarboxylic acid and reacting a polybasic acid anhydride with some or all of the secondary hydroxyl groups produced by this reaction. Containing resin.
(6) A polyfunctional epoxy compound is reacted with a compound having one reactive group other than a hydroxyl group that reacts with two or more hydroxyl groups and an epoxy group in one molecule, and an unsaturated group-containing monocarboxylic acid. A carboxyl group-containing photosensitive resin obtained by reacting the obtained reaction product with a polybasic acid anhydride.
(7) Obtained by reacting a reaction product of a resin having a phenolic hydroxyl group with an alkylene oxide or a cyclic carbonate with an unsaturated group-containing monocarboxylic acid, and reacting the resulting reaction product with a polybasic acid anhydride. Carboxyl group-containing photosensitive resin.
(8) A reaction product obtained by reacting a polyfunctional epoxy compound, a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule, and an unsaturated group-containing monocarboxylic acid. A carboxyl group-containing photosensitive resin obtained by reacting an anhydride group of a polybasic acid anhydride with an alcoholic hydroxyl group.

  In addition to cellulose nanofibers, a binder component, and a layered silicate, other conventional compounding components can be appropriately blended with the printed wiring board material of the present invention.

Examples of other conventional compounding components include a curing catalyst, a photopolymerization initiator, a colorant, and an organic solvent.
The curing catalyst is mainly for curing a thermosetting resin among curable resins. For example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2- Imidazole derivatives such as phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4- (dimethylamino) Amine compounds such as -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl-N, N-dimethylbenzylamine, hydrazine compounds such as adipic acid dihydrazide, sebacic acid dihydrazide; Phosphorylation of phenylphosphine, etc. Things and the like. Examples of commercially available products include 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (manufactured by Shikoku Kasei Kogyo Co., Ltd.), U-CAT3503N, U-CAT3502T, DBU, DBN, U-CATSA102, U- CAT5002 (manufactured by San Apro Co., Ltd.) and the like may be mentioned, and they may be used alone or in combination of two or more. Similarly, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6 S-triazine derivatives such as -diamino-S-triazine / isocyanuric acid adduct and 2,4-diamino-6-methacryloyloxyethyl-S-triazine / isocyanuric acid adduct can also be used.

  In addition, the photopolymerization initiator is for curing the photocurable resin among the curable resins, for example, benzoin and benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether. Acetophenones such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone; 2-methyl -1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2- (dimethylamino) ) -2-[(4-Methylphenyl) methyl Aminoalkylphenones such as -1- [4- (4-morpholinyl) phenyl] -1-butanone; anthraquinones such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-tertiarybutylanthraquinone, 1-chloroanthraquinone; Thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, and 2,4-diisopropylthioxanthone; Ketals such as acetophenone dimethyl ketal and benzyldimethyl ketal; Benzophenones such as benzophenone; or xanthone (2,6-dimethoxybenzoyl) -2,4,4-pentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-tri Chill diphenylphosphine oxide, phosphine oxide such as ethyl 2,4,6-trimethylbenzoylphenyl phosphinate Nate; various peroxides, and the like titanocene initiators. These are photosensitized like tertiary amines such as N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylaminobenzoate, triethylamine, triethanolamine and the like. You may use together with an agent etc. These photopolymerization initiators can be used alone or in combination of two or more.

  As the colorant, a known and conventional one represented by a color index as a color pigment or dye can be used. For example, Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4 15: 6, 16, 60, Solvent Blue 35, 63, 68, 70, 83, 87, 94, 97, 122, 136 , 67, 70, Pigment Green 7, 36, 3, 5, 20, 28, Solvent Yellow 163, Pigment Yellow 24, 108, 193, 147, 199, 202, 110, 109, 139 179 185 93, 94, 95, 128, 155, 166, 180, 120, 151, 154, 156, 175, 181, 1, 2, 3, 4, 5, 6, 9, 10, 12, 61, 62, 62: 1, 65, 73, 74, 75, 97, 100, 104, 105, 111, 116, 167, 168, 169, 182 , 183, 12, 13, 14, 16, 17, 55, 63, 81, 83, 87, 126, 127, 152, 170, 172, 174, 176, 188, 198, Pigment Orange 1, 5, 13, 14 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 61, 63, 64, 71, 73, Pigment Red 1, 2, 3, 4, 5, 6, 8, 9 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 112, 114, 146, 147, 151, 170, 184, 187, 188, 193, 210, 245, 253, 258, 266 267, 268, 269, 37, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53 1,5 : 2, 57: 1, 58: 4, 63: 1, 63: 2, 64: 1, 68, 171, 175, 176, 185, 208, 123, 149, 166, 178, 179, 190, 194, 224 254, 255, 264, 270, 272, 220, 144, 166, 214, 220, 221, 242, 168, 177, 216, 122, 202, 206, 207, 209, Solvent Red 135, 179, 149, 150 , 52, 207, Pigment Violet 19, 23, 29, 32, 36, 38, 42, Solvent Violet 13, 36, Pigment Brown 23, 25, Pigment Black 1, 7, and the like.

  Examples of organic solvents include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, diethylene glycol Glycol ethers such as monoethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monoethyl ether; esters such as ethyl acetate, butyl acetate, cellosolve acetate, diethylene glycol monoethyl ether acetate and esterified products of the above glycol ethers; Alcohols such as ethanol, propanol, ethylene glycol, propylene glycol; octa Aliphatic hydrocarbons such as decane may be mentioned petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, a petroleum solvent or the like, such as solvent naphtha.

Moreover, additives, such as a defoaming and leveling agent, a thixotropy imparting agent / thickening agent, a coupling agent, a dispersant, and a flame retardant, may be included as necessary.
Antifoaming and leveling agents include compounds such as silicone, modified silicone, mineral oil, vegetable oil, aliphatic alcohol, fatty acid, metal soap, fatty acid amide, polyoxyalkylene glycol, polyoxyalkylene alkyl ether, polyoxyalkylene fatty acid ester, etc. Etc. can be used.

  As the thixotropy imparting agent / thickening agent, fine particle silica, silica gel, amorphous inorganic particles, polyamide-based additive, modified urea-based additive, wax-based additive and the like can be used.

  As the coupling agent, alkoxy group is methoxy group, ethoxy group, acetyl, etc., and reactive functional group is vinyl, methacryl, acrylic, epoxy, cyclic epoxy, mercapto, amino, diamino, acid anhydride, ureido, sulfide, Isocyanates and the like, for example, vinyl silane compounds such as vinyl ethoxylane, vinyl trimethoxysilane, vinyl tris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxylane, γ-aminopropyltrimethoxylane,系 -β- (aminoethyl) γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) γ-aminopropylmethyldimethoxysilane, amino-based silane compounds such as γ-ureidopropyltriethoxysilane, and γ-glycid Xipropyltrimethoxy Epoxy silane compounds such as silane, β- (3,4-epoxycyclohexyl) ethyltrimethoxylane, γ-glycidoxypropylmethyldiethoxysilane, mercapto silane compounds such as γ-mercaptopropyltrimethoxysilane, Silane coupling agents such as phenylamino silane compounds such as phenyl-γ-aminopropyltrimethoxysilane, isopropyl triisostearoylated titanate, tetraoctyl bis (ditridecyl phosphite) titanate, bis (dioctyl pyrophosphate) oxyacetate titanate , Isopropyltridodecylbenzenesulfonyl titanate, isopropyltris (dioctylpyrophosphate) titanate, tetraisopropylbis (dioctylphosphite) titanate, La (1,1-diallyloxymethyl-1-butyl) bis- (ditridecyl) phosphite titanate, bis (dioctylpyrophosphate) ethylene titanate, isopropyltrioctanoyl titanate, isopropyldimethacrylisostearoyl titanate, isopropyltristearoyl diacryl Titanate, isopropyl tri (dioctyl phosphate) titanate, isopropyl tricumylphenyl titanate, dicumylphenyloxyacetate titanate, diisostearoyl ethylene titanate, etc., ethylenically unsaturated zirconate-containing compound, neoalkoxy zirconate-containing compound , Neoalkoxytris neodecanoyl zirconate, neoalkoxytris (dodecyl) benzenes Lulphonyl zirconate, neoalkoxy tris (dioctyl) phosphate zirconate, neoalkoxy tris (dioctyl) pyrophosphate zirconate, neoalkoxy tris (ethylenediamino) ethyl zirconate, neoalkoxy tris (m-amino) phenyl zirconate, tetra (2,2-diallyloxymethyl) butyl, di (ditridecyl) phosphito zirconate, neopentyl (diallyl) oxy, trineodecanoyl zirconate, neopentyl (diallyl) oxy, tri (dodecyl) benzene-sulfonyl zirconate, neopentyl (Diallyl) oxy, tri (dioctyl) phosphatozirconate, neopentyl (diallyl) oxy, tri (dioctyl) pyro-phosphatozirconate, neopentyl (di Ryl) oxy, tri (N-ethylenediamino) ethyl zirconate, neopentyl (diallyl) oxy, tri (m-amino) phenyl zirconate, neopentyl (diallyl) oxy, trimethacryl zirconate, neopentyl (diallyl) oxy, triacryl Zirconate, dineopentyl (diallyl) oxy, diparaaminobenzoyl zirconate, dineopentyl (diallyl) oxy, di (3-mercapto) propionic zirconate, zirconium (IV) 2,2-bis (2-propenolatomethyl) Zirconate coupling agents such as butanolato, cyclodi [2,2- (bis-2-propenolatomethyl) butanolato] pyrophosphato-O, O, diisobutyl (oleyl) acetoacetylaluminate, alkylacetoacetate Diisopropylate aluminate coupling agents such like.

  Dispersants include polycarboxylic acid-based, naphthalene sulfonic acid formalin condensation-based, polyethylene glycol, polycarboxylic acid partial alkyl ester-based, polyether-based, polyalkylene polyamine-based polymeric dispersants, alkyl sulfonic acid-based, four Low molecular weight dispersants such as secondary ammonium series, higher alcohol alkylene oxide series, polyhydric alcohol ester series and alkylpolyamine series can be used.

  Flame retardants include hydrated metal such as aluminum hydroxide and magnesium hydroxide, red phosphorus, ammonium phosphate, ammonium carbonate, zinc borate, zinc stannate, molybdenum compound, bromine compound, chlorine compound, phosphate ester Phosphorus-containing polyol, phosphorus-containing amine, melamine cyanurate, melamine compound, triazine compound, guanidine compound, silicon polymer, and the like can be used.

  Other ingredients include photoacid generators such as diazonium salts, sulfonium salts, iodonium salts, photobase generators such as carbamate compounds, α-aminoketone compounds, O-acyloxime compounds, and inorganic fillers such as barium sulfate and spherical silica. And organic fillers such as silicon powder, nylon powder and fluorine powder, radical scavengers, ultraviolet absorbers, peroxide decomposers, thermal polymerization inhibitors, adhesion promoters, rust inhibitors and the like.

  The printed wiring board material according to the present invention having the configuration as described above can be suitably used for the solder resist and the core material, and can be suitably used for the interlayer insulating material of the multilayer printed wiring board, Thereby, in the obtained printed wiring board, the expected effect of the present invention can be obtained. Further, when the present invention is applied to a printed wiring board material, for example, a method of forming the cellulose nanofibers into a sheet shape, impregnating a binder component into the sheet-like cellulose nanofibers, and drying to prepare a prepreg. Can be used.

  FIG. 1 is a partial cross-sectional view showing a configuration example of a multilayer printed wiring board according to the present invention. The illustrated multilayer printed wiring board can be manufactured, for example, as follows. First, a through hole is formed in the core substrate 2 on which the conductor pattern 1 is formed. The through hole can be formed by an appropriate means such as a drill, a die punch, or laser light. Then, a roughening process is performed using a roughening agent. Generally, the roughening treatment is performed by swelling with an organic solvent such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, methoxypropanol, or an alkaline aqueous solution such as caustic soda or caustic potash, and then dichromate and permanganic acid. It is carried out using an oxidizing agent such as salt, ozone, hydrogen peroxide / sulfuric acid or nitric acid.

  Next, the conductor pattern 3 is formed by a combination of electroless plating or electrolytic plating. The step of forming the conductor layer by electroless plating is a step of immersing in an aqueous solution containing a plating catalyst, adsorbing the catalyst, and then immersing in a plating solution to deposit the plating. A predetermined circuit pattern is formed on the conductor layer on the surface of the core substrate 2 in accordance with a conventional method (subtractive method, semi-additive method, etc.), and a conductor pattern 3 is formed on both sides as shown. At this time, a plated layer is also formed in the through hole, and as a result, the connection portion 4 of the conductor pattern 3 of the multilayer printed wiring board and the connection portion 1a of the conductor pattern 1 are electrically connected. Through hole 5 is formed.

  Next, for example, after applying a thermosetting composition by an appropriate method such as a screen printing method, a spray coating method, or a curtain coating method, the interlayer insulating layer 6 is formed by heating and curing. When a dry film or prepreg is used, the interlayer insulating layer 6 is formed by laminating or hot plate pressing and heat curing. Next, vias 7 for electrically connecting the connection portions of the conductor layers are formed by appropriate means such as laser light, and the conductor pattern 8 is formed by the same method as the conductor pattern 3. Further, the interlayer insulating layer 9, the via 10 and the conductor pattern 11 are formed by the same method. Then, a multilayer printed wiring board is manufactured by forming the solder resist layer 12 in the outermost layer. In the above, the example in which the interlayer insulating layer and the conductor layer are formed on the multilayer substrate has been described. However, a single-sided substrate or a double-sided substrate may be used instead of the multilayer substrate.

Hereinafter, the present invention will be described in more detail with reference to examples. In addition, all the numbers in the following table | surfaces show a mass part.
[Synthesis Example 1]
(Varnish 1)
In a 2 liter separable flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel and nitrogen introduction tube, 900 g of diethylene glycol dimethyl ether as a solvent and t-butylperoxy 2-ethylhexanoate as a polymerization initiator 21.4 g (manufactured by NOF Corporation, trade name: Perbutyl O) was added and heated to 90 ° C. After heating, 309.9 g of methacrylic acid, 116.4 g of methyl methacrylate, and 109.8 g of lactone-modified 2-hydroxyethyl methacrylate (manufactured by Daicel Corporation, trade name: Plaxel FM1) were used as a polymerization initiator. Along with 21.4 g of certain bis (4-t-butylcyclohexyl) peroxydicarbonate (manufactured by NOF Corporation, trade name: Parroyl TCP), it was added dropwise over 3 hours. Further, this was aged for 6 hours to obtain a carboxyl group-containing copolymer resin. These reactions were performed in a nitrogen atmosphere.

  Next, to the obtained carboxyl group-containing copolymer resin, 363.9 g of 3,4-epoxycyclohexylmethyl acrylate (manufactured by Daicel Corporation, trade name: Cyclomer A200), dimethylbenzylamine 3 as a ring-opening catalyst .6 g and 1.80 g of hydroquinone monomethyl ether as a polymerization inhibitor were added, and the mixture was heated to 100 ° C. and stirred to carry out an epoxy ring-opening addition reaction. After 16 hours, a solution containing 53.8% by mass (nonvolatile content) of a carboxyl group-containing resin having a solid acid value of 108.9 mgKOH / g and a weight average molecular weight of 25,000 was obtained.

[Synthesis Example 2]
(Varnish 2)
A flask equipped with a thermometer, stirrer, dropping funnel and reflux condenser is charged with diethylene glycol monoethyl ether acetate as a solvent and azobisisobutyronitrile as a catalyst and heated to 80 ° C. in a nitrogen atmosphere. Then, a monomer in which methacrylic acid and methyl methacrylate were mixed at a molar ratio of 0.40: 0.60 was dropped over about 2 hours. Furthermore, after stirring this for 1 hour, the temperature was raised to 115 ° C. and deactivated to obtain a resin solution.

  After cooling the resin solution, tetrabutylammonium bromide was used as a catalyst, and butyl glycidyl ether was added at a molar ratio of 0.40 at 95 to 105 ° C. for 30 hours. Addition reaction with an equal volume and cooling.

  Furthermore, tetrahydrophthalic anhydride was subjected to addition reaction at a molar ratio of 0.26 under the condition of 95 to 105 ° C. for 8 hours with respect to the OH group of the resin obtained above. This was taken out after cooling to obtain a solution containing 50% by mass (nonvolatile content) of a carboxyl group-containing resin having a solid acid value of 78.1 mgKOH / g and a mass average molecular weight of 35,000.

[Synthesis Example 3]
(Varnish 3)
In a flask equipped with a thermometer, a stirrer, a dropping funnel and a reflux condenser, 210 g of cresol novolac type epoxy resin (DIC Corporation, Epicron N-680, epoxy equivalent = 210) and carbitol acetate 96 as a solvent .4 g was added and dissolved by heating. Subsequently, 0.1 g of hydroquinone as a polymerization inhibitor and 2.0 g of triphenylphosphine as a reaction catalyst were added thereto. This mixture was heated to 95-105 ° C., 72 g of acrylic acid was gradually added dropwise, and the mixture was reacted for about 16 hours until the acid value became 3.0 mgKOH / g or less. The reaction product was cooled to 80 to 90 ° C., 76.1 g of tetrahydrophthalic anhydride was added, and about 6 hours until the absorption peak (1780 cm ⁻¹ ) of the acid anhydride disappeared by infrared absorption analysis. Reacted. To this reaction solution, 96.4 g of aromatic solvent ipsol # 150 manufactured by Idemitsu Kosan Co., Ltd. was added, diluted, and taken out. The thus obtained carboxyl group-containing photosensitive polymer solution had a nonvolatile content of 65 mass% and a solid content acid value of 78 mgKOH / g.

[Preparation of cellulose nanofiber dispersion]
Cellulose nanofiber (manufactured by Sugino Machine Co., Ltd., BiNFi-s (binfis) 10% by weight cellulose, number average fiber diameter 80 nm) is subjected to dehydration filtration, and 10 times the amount of carbitol acetate by weight of the filtrate is added for 30 minutes. After stirring, it was filtered. This replacement operation was repeated three times, and 10 times the weight of the filtrate was added with carbitol acetate to prepare a 10% by mass cellulose nanofiber dispersion.

[Production of evaluation sheet]
In accordance with the description in Table 1 below, each component was blended, stirred, and dispersed by a three roll to prepare each composition. The addition amount of the cellulose nanofiber and the layered silicate was 10% by mass with respect to the total amount of the composition excluding the solvent. Next, this composition was printed on a copper foil having a thickness of 18 μm on the entire surface by a screen printing method, and cured in a hot air circulation type drying furnace at 140 ° C. for 30 minutes. Thereafter, the copper foil was removed to prepare a sheet having a thickness of 50 μm.

[Evaluation of linear expansion coefficient]
The sheet prepared above was cut into 3 mm width × 30 mm length. Using TMA (Thermal Mechanical Analysis) “EXSTAR6000” manufactured by SII, the temperature was increased from room temperature to 200 ° C. at a rate of 5 ° C./min in a tensile mode, 10 mm between chucks, 30 mN load, and then 200 ° C. The temperature was decreased from 5 to 20 ° C. at 5 ° C./min. Then, the linear expansion coefficient was calculated | required from the measured value of 30 to 100 degreeC when it heated up at 5 degree-C / min from 20 degreeC to 200 degreeC. The evaluation results are shown in Table 1.

* 1) Thermosetting compound 1: Epicote 828, manufactured by Mitsubishi Chemical Corporation * 2) Thermosetting compound 2: Epicote 807, manufactured by Mitsubishi Chemical Corporation * 3) Curing catalyst 1: 2MZ-A Shikoku Chemicals Co., Ltd. * 4) Colorant: Phthalocyanine Blue
* 5) Layered silicate: Lucentite STN Co-op Chemical Co., Ltd. * 6) Organic solvent: Carbitol acetate

  In accordance with the description in Table 2 below, each component was blended, stirred, and dispersed by a three roll to prepare each composition. The addition amount of the cellulose nanofiber and the layered silicate was 10% by mass with respect to the total amount of the composition excluding the solvent. Next, this composition was printed on a copper foil having a thickness of 18 μm on the entire surface by a screen printing method, dried in a hot air circulation drying oven at 100 ° C. for 30 minutes, and then at 170 ° C. for 60 minutes. And cured. Thereafter, the copper foil was removed, and the linear expansion coefficient of the obtained sheet having a thickness of 50 μm was measured.

* 7) Thermosetting compound 3: Unidic V-8000 (solid content 40% by mass) manufactured by DIC Corporation * 8) Thermosetting compound 4: Denacol EX-830 manufactured by Nagase ChemteX Corporation * 9) Curing Catalyst 2: Triphenylphosphine

  According to the description in Table 3 below, each component was blended and melt-kneaded at 180 ° C. for 10 minutes at a rotation speed of 70 rpm using a kneader (laboplast mill, manufactured by Toyo Seiki Co., Ltd.). The addition amount of the cellulose nanofiber and the layered silicate was 10% by mass with respect to the total amount of the composition excluding the solvent. The obtained kneaded product was hot-pressed at 190 ° C., 0.5 MPa for 3 minutes, and 20 MPa for 1 minute using a press machine (Lab Press P2-30T, manufactured by Toyo Seiki Co., Ltd.), and further at 23 ° C. Cold pressing was performed at 0.5 MPa for 1 minute. Thus, the linear expansion coefficient of the obtained sheet having a thickness of 50 μm was measured.

* 10) Thermoplastic resin 1: Novatec PP BC03L manufactured by Nippon Polypro Co., Ltd.

  Each component was blended according to the description in Table 4 below, and melt-kneaded at 150 ° C. for 10 minutes at a rotation speed of 70 rpm using a kneader (laboplast mill, manufactured by Toyo Seiki Co., Ltd.). The addition amount of the cellulose nanofiber and the layered silicate was 10% by mass with respect to the total amount of the composition excluding the solvent. The obtained kneaded product was hot-pressed at 160 ° C., 0.5 MPa for 3 minutes, and 20 MPa for 1 minute using a press machine (Lab Press P2-30T, manufactured by Toyo Seiki Co., Ltd.), and further at 23 ° C. Cold pressing was performed at 0.5 MPa for 1 minute. Thus, the linear expansion coefficient of the obtained sheet having a thickness of 50 μm was measured.

* 11) Thermoplastic resin 2: Novatec LD LC561, manufactured by Nippon Polyethylene Co., Ltd.

  In accordance with the description in Table 5 below, each component was blended, stirred, and dispersed by a three roll to prepare each composition. The addition amount of the cellulose nanofiber and the layered silicate was 10% by mass with respect to the total amount of the composition excluding the solvent. Next, this composition was printed on a copper foil having a thickness of 18 μm on the entire surface by a screen printing method, dried in a hot air circulating drying oven at 120 ° C. for 10 minutes, and then at 250 ° C. for 30 minutes. And cured. Thereafter, the copper foil was removed, and the linear expansion coefficient of the obtained sheet having a thickness of 50 μm was measured.

* 12) Thermoplastic resin 3: Socsea SOXR-OB Varnish manufactured by Nippon Kogyo Paper Industries Co., Ltd. (solid content: 70% by mass)

In accordance with the description in Table 6 below, each component was blended, stirred, and dispersed with a three roll to prepare each composition. The addition amount of the cellulose nanofiber and the layered silicate was 10% by mass with respect to the total amount of the composition excluding the solvent. Next, this composition was printed on a copper foil having a thickness of 18 μm on the entire surface by a screen printing method, and cured by irradiating an integrated light amount of ² J / cm ² at a wavelength of 350 nm with a metal halide lamp. Thereafter, the copper foil was removed, and the linear expansion coefficient of the obtained sheet having a thickness of 50 μm was measured.

* 13) Photocurable compound 1: Bisphenol A type epoxy acrylate Mitsubishi Chemical Co., Ltd. * 14) Photocurable compound 2: Trimethylolpropane triacrylate * 15) Photocurable compound 3: Kayamar PM2 Nippon Kayaku Co., Ltd. * 16) Photocurable compound 4: Light ester HO Kyoeisha Chemical Co., Ltd. * 17) Photopolymerization initiator 1: 2-ethylanthraquinone

In accordance with the description in Table 7 to Table 9 below, each component was blended, stirred, and dispersed with a three roll to prepare each composition. The addition amount of the cellulose nanofiber and the layered silicate was 10% by mass with respect to the total amount of the composition excluding the solvent. Next, this composition was printed on a copper foil having a thickness of 18 μm on the entire surface by a screen printing method, and dried at 80 ° C. for 30 minutes in a hot air circulation drying furnace. Next, using a negative pattern capable of covering the edge of the test substrate, the printed wiring board exposure machine HMW-680GW (manufactured by Oak Manufacturing Co., Ltd.) is exposed with an integrated light amount of 700 mJ / cm ² and 1% at 30 ° C. The aqueous sodium carbonate solution was developed for 60 seconds with a developing machine for printed wiring boards, and the edge portion was removed. Subsequently, thermosetting was performed at 150 ° C. for 60 minutes in a hot air circulation drying oven. Thereafter, the copper foil was removed, and the linear expansion coefficient of the obtained sheet having a thickness of 50 μm was measured.

* 18) Curing catalyst 3: Finely ground melamine * 19) Curing catalyst 4: Dicyandiamide * 20) Photopolymerization initiator 2: Irgacure 907 manufactured by BASF * 21) Photocurable compound 5: Dipentaeryth Little tetraacrylate * 22) Thermosetting compound 5: TEPIC-H Nissan Chemical Co., Ltd.

  As described in detail above, it has been confirmed that the linear expansion coefficient is drastically reduced according to the insulating material using the cellulose nanofiber and the layered silicate in combination.

1, 3, 8, 11 Conductor pattern 2 Core substrate 1a, 4 Connection portion 5 Through hole 6, 9 Interlayer insulating layer 7, 10 Via 12 Solder resist layer

Claims (7)

A composition comprising a binder component, a cellulose nanofiber having a number average fiber diameter of 3 nm to 1000 nm, and a layered silicate ,
The printed wiring board material, wherein the total amount of the cellulose nanofiber and the layered silicate is 10.7% by mass or less based on the total amount of the composition excluding the solvent .   The printed wiring board material according to claim 1, wherein the binder component is a thermoplastic resin.   The printed wiring board material according to claim 1, wherein the binder component is a curable resin.   It is an object for solder resists, The printed wiring board material as described in any one of Claims 1-3.   It is for core materials, The printed wiring board material as described in any one of Claims 1-3.   The printed wiring board material according to any one of claims 1 to 3, which is used for an interlayer insulating material of a multilayer printed wiring board. A printed wiring board comprising the printed wiring board material according to claim 1.