WO2014175244A1

WO2014175244A1 - Printed-circuit-board material and printed circuit board using same

Info

Publication number: WO2014175244A1
Application number: PCT/JP2014/061235
Authority: WO
Inventors: 武徳角谷; 柴田　大介; 宇敷　滋; 遠藤　新; 崇夫三輪
Original assignee: 太陽ホールディングス株式会社
Priority date: 2013-04-23
Filing date: 2014-04-22
Publication date: 2014-10-30
Also published as: KR102192598B1; TWI621380B; CN105122953A; KR20160002810A; TW201513742A; CN105122953B

Abstract

This invention provides the following: a printed-circuit-board material wherein the top surface of a copper or other metal film is resistant to smearing, and even if smearing does occur, said smearing is easy to remove; and a printed circuit board using said printed-circuit-board material. Said printed-circuit-board material contains the following: a binder component; cellulose nanofibers having a number-average diameter between 3 and 1,000 nm, inclusive; and an acrylic-copolymer compound. Said printed-circuit-board material is suitable for use as a solder resist or as an interlayer insulation material for multilayer printed circuit boards. This printed circuit board uses said printed-circuit-board material.

Description

Printed wiring board material and printed wiring board using the same

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. 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 Documents

1, 2, and 3).

By the way, when forming a circuit, a laser is used to form a hole (via) for interlayer conduction, but there is a problem that smear (residue) tends to remain on the surface (via bottom) of a metal foil such as copper. . If the desmear process is reinforced to remove the smear at the bottom of the via, the insulating layer is eroded, making it difficult to fill the via bottom and the inside of the via with plating (see, for example, Patent Document 4).

Also, after removing a part of the solder resist to expose the circuit, components are mounted with solder or the like and the wiring is taken out. When the circuit is exposed, a laser processing method is used to expose the circuit by removing the solder resist at the desired part by laser processing, in addition to the photo development method using a photosensitive solder resist, which is a general technique. ing. However, the laser processing method has a problem that smears (residues) are likely to remain as in the case of the hole (via) for interlayer conduction (see, for example, Patent Document 5).

JP 2006-182991 A (Claims etc.) JP 2013-36042 A (Claims etc.) JP 08-269172 A (Claims etc.) JP 2009-200301 A (Claims etc.) JP 2010-031216 A (claims, paragraphs [0079] to [0086], etc.)

An object of the present invention is to provide a printed wiring board material that does not easily cause smear on the surface of a metal foil such as copper and that can be easily removed even if it occurs, and a printed wiring board using the printed wiring board material.

As a result of intensive studies, the present inventors have found that the above-described problems can be solved by using a material containing cellulose nanofibers and an acrylic copolymer compound as a printed wiring board material, thereby completing the present invention. It was.

That is, the printed wiring board material of the present invention is characterized by including a binder component, cellulose nanofibers having a number average fiber diameter of 3 nm to 1000 nm, and an acrylic copolymer compound.

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 preferably contains a layered silicate. Moreover, it is preferable that the printed wiring board material of this invention contains any one or both of a silicone compound and a fluorine compound. Furthermore, in the printed wiring board material of this invention, it is preferable that the number average fiber diameter of the said cellulose nanofiber is 3 nm or more and less than 1000 nm, and also contains a cellulose fiber with a number average fiber diameter of 1 micrometer or more.

Furthermore, in the printed wiring board material of the present invention, it is preferable that the cellulose nanofiber has a carboxylate in its structure. Furthermore, in the printed wiring board material of the present invention, it is preferable that the cellulose nanofiber is manufactured from lignocellulose.

The printed wiring board material of the present invention can be suitably used for solder resists 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, a printed wiring board material containing cellulose nanofibers and an acrylic copolymer compound is less likely to cause smear on the surface of a metal foil such as copper and is generated. Even so, a printed wiring board material that can be easily removed and a printed wiring board using the same can be realized.

It is a fragmentary sectional view which shows one structural example of the multilayer printed wiring board which concerns on this invention. It is explanatory drawing which shows the preparation methods of the board | substrate for the smear removal property evaluation of the soldering resist and interlayer insulation material in an Example. It is explanatory drawing which shows the preparation methods of the board | substrate for the evaluation of the interlayer insulation material in an Example. It is explanatory drawing which shows the preparation methods of the board | substrate for evaluation of the core material in an Example. It is explanatory drawing which shows the preparation methods of the board | substrate for evaluation of the other core material in an Example.

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 contains a binder component, cellulose nanofibers having a number average fiber diameter of 3 nm to 1000 nm, and an acrylic copolymer compound. The cellulose nanofiber can be obtained as follows.

(Cellulose nanofibers with a number average fiber diameter of 3 nm to 1000 nm)
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 or the like are mechanically treated with a high-pressure homogenizer or the like, and 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, by repeatedly grinding or crushing this with a grinder or the like, cellulose nanofibers having a fiber diameter of about 10 to 100 nm can be obtained.

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 of obtaining cellulose nanofibers by unraveling the fibers by exposing the raw materials such as pulp to high temperature and high pressure steam.

Further, in the treatment with the phosphate, etc., the surface of the raw material such as the pulp is phosphorylated to weaken the bonding force between the cellulose fibers, and then the refiner treatment (grinding or crushing treatment) is performed. This is a treatment method for unraveling the fibers and obtaining cellulose 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 (such as the above-mentioned grinder).

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 cannot be produced substantially less than 3 nm, and when it exceeds 1000 nm, the dispersibility with the binder component 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 0.1 to 80% by mass, more preferably 0.2 to 70% by mass, based on the total amount of the composition excluding the solvent. When the blending amount of the cellulose nanofiber is 0.1% by mass or more, the desired effect of the present invention can be obtained satisfactorily. On the other hand, in the case of 80 mass% or less, film forming property improves.

Examples of the acrylic copolymer compound include poly (meth) acrylate, modified poly (meth) acrylate and the like, and specific examples thereof include BYK-350, BYK-352, BYK- manufactured by BYK Chemie Japan Co., Ltd. 354, BYK-355, BYK-356, BYK-358N, BYK-361N, BYK-380N, BYK-381, BYK-392, BYK-394, BYK-3440, BYK-3550, BYK-SILCLEAN3700, Disperbyk-2000, Disperbyk-2001, Disperbyk-2020, Disperbyk-2050, Disperbyk-2070, OX-880EF, OX-881, OX-883, OX-883HF, OX-77EF, OX-7 manufactured by Enomoto Chemical Co., Ltd. 0,1970,230, LF-1980, LF-1982, LF-1983, LF-1984, LF-1985, manufactured by Kyoeisha Chemical Co., Ltd. of the (stock) Polyflow No. 7, Polyflow No. 50E, Polyflow No. 50EHF, Polyflow No. 54N, Polyflow No. 75, Polyflow No. 77, Polyflow No. 85, Polyflow No. 85HF, Polyflow No. 90, polyflow no. 90D-50, Polyflow No. 95, Polyflow PW-95, Polyflow No. 99C etc. are mentioned, but it is not limited to these. These may be used individually by 1 type, or may use 2 or more types together.

In addition, the amount of the acrylic copolymer compound used in the present invention is usually a ratio that is usually used. For example, it is preferably 0.01 to 20 parts by weight, more preferably 100 parts by weight of the binder component. Is 0.01 to 10 parts by mass, and more preferably 0.05 to 3 parts by mass. If the amount of the acrylic copolymer compound is too small, the desired effect of the present invention may not be obtained. If it is too much, some liquid components of the acrylic copolymer compound are cured from the cured product. Since a so-called bleed phenomenon that oozes out to the surface of the object occurs, it is not preferable anyway.

(Binder component)
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 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, poly Midimide, 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.

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 Resin, 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) isocyanur , Triglycidyl tris (2-hydroxyethyl) isocyanurate, phenol novolac resin, cresol novolac resin, bisphenol A novolac resin and other novolak type phenol resins, unmodified resole phenol resin, tung oil, linseed oil, walnut oil, etc. Phenol resin such as resol type phenol resin such as modified oil-modified resol phenol resin, phenoxy resin, urea (urea) resin, triazine ring-containing resin such as 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, A polyazomethine resin, a thermosetting polyimide, etc. are mentioned.

The radically polymerizable photocurable resin may be any resin that is cured by irradiation with active energy rays and exhibits electrical insulation, and in particular, a compound having one or more ethylenically unsaturated bonds in the molecule is preferably used. It is done. 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-ethoxymethylacrylamide (Meth) acrylamides such as rilamide 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; Alkyl such as methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate Coxyalkylene glycol mono (meth) acrylates; ethylene glycol di (meth) acrylate, butanediol di (meth) acrylates, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, tri Alkylene polyol poly (meth) acrylates such as methylolpropane 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 (Meth) 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.

As the cationic polymerizable photocurable resin, an alicyclic epoxy compound, an oxetane compound, a vinyl ether compound, or 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 Cyclohexene oxide, 3,4-epoxycyclohexylmethyl alcohol and alicyclic epoxy compounds having an epoxy group such as 3,4-epoxycyclohexyl ethyl trimethoxy silane. Examples of commercially available products include Celoxide 2000, Celoxide 2021, Celoxide 3000, EHPE 3150 manufactured by Daicel Corporation, Epomic VG-3101 manufactured by Mitsui Chemicals, Inc., E-1031S manufactured by Mitsubishi Chemical Corporation, and Mitsubishi Gas Chemical ( And TETRAD-X and TETRAD-C manufactured by Nippon Soda Co., Ltd. and EPB-27 manufactured by Nippon Soda Co., Ltd.

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 bisphenol Oxetane compounds such as ethers of calixarenes, calixresorcinarenes, or resins having a hydroxyl group such as silsesquioxane, and copolymers of unsaturated monomers having an oxetane ring and alkyl (meth) acrylate It is done. 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 a cyclic ether group 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, cyclohexanedimethanol divinyl ether, α and / or β position And vinyl ether compounds having a substituent such as an alkyl group and an allyl group. It is. 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.

Further, 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 alkaline aqueous 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 the printed wiring board material of the present invention, in addition to cellulose nanofibers, a binder component, and an acrylic copolymer compound, other conventional compounding components can be appropriately blended depending on the application.

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 and 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 these may be used alone or in admixture 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, 2,4-diisopropylthioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenones such as benzophenone; or Xanthones; (2,6-dimethoxybenzoyl) -2,4,4-pentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-to Methyl benzoyl diphenyl phosphine 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, 16 , 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. , 3: 1, 53: 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; Mention may be made of petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, a petroleum solvent or the like, such as solvent naphtha; down, aliphatic hydrocarbons such as decane.

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 thixotropy imparting agent / thickening agent, clay minerals such as kaolinite, smectite, montmorillonite, bentonite, talc, mica, zeolite, etc., silica gel, silica gel, amorphous inorganic particles, polyamide additives, modified urea additives, Wax-based additives 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, γ-glycid Xylpropyltrimeth 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, Tora (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) benzene Sulfonyl 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 ( Allyl) 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 DOO 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, barium sulfate, spherical silica, hydrotalcite. And inorganic 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 applied to a solder resist, and can be suitably used for an interlayer insulating material of a multilayer printed wiring board. In the obtained printed wiring board, the desired effect of the present invention can be obtained. Furthermore, when the present invention is applied to a printed wiring board material, for example, there is a method of forming a prepreg by forming the cellulose nanofibers into a sheet shape, impregnating the sheet-like cellulose nanofibers with a binder component, and drying. 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 carried out by swelling with an organic solvent such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, or methoxypropanol, or an alkaline aqueous solution such as caustic soda or caustic potash. 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, by 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.

The printed wiring board material of the present invention preferably further contains a layered silicate. By blending cellulose nanofiber and layered silicate in combination, the linear expansion coefficient can be significantly reduced with a smaller amount of blending than when either one is blended.

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.

Further, as a layered silicate organic agent used in the present invention, any general onium salt may be used, and it is disclosed in JP-A-2004-107541 from the viewpoint of heat resistance. 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 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 the layered silicate is sufficiently solvated with water, alcohol or the like, an organophilic agent is added and stirred to replace the inorganic cation between 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. 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 even more preferably at a temperature range of 15 to 80 ° C.

The amount of the layered silicate used in the present invention is preferably 0.02 to 48% by mass, more preferably 0.04 to 42% by mass, based on the total amount of the composition excluding the solvent. 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. %.

Further, the printed wiring board material of the present invention preferably contains one or both of a silicone compound and a fluorine compound. By including one or both of the silicone compound and the fluorine compound, it is possible to obtain an effect of suppressing the occurrence of migration between holes.

(Silicone compound)
Examples of the silicone compound include polydimethylsiloxane, polyalkylphenylsiloxane, alkyl-modified silicone oil, polyether-modified silicone oil, polyalkylsiloxane, polymethylsilsesquioxane, polyalkylhydrogensiloxane, polyalkylalkenylsiloxane, and polymethylphenyl. Examples thereof include siloxane, aralkyl-modified silicone oil, and alkylaralkyl-modified silicone oil. Commercially available products include BYK-300, BYK-302, BYK-306, BYK-307, BYK-310, BYK-313, BYK-330, BYK-331, BYK-333, BYK-337, BYK-341, BYK -344, BYK-370, BYK375 (above, manufactured by Big Chemie Japan Co., Ltd.), KS-66, KS-69, FZ-2110, FZ-2166, FZ-2154, FZ-2120, L-720, L- 7002, SH8700, L-7001, FZ-2123, SH8400, FZ-77, FZ-2164, FZ-2203, FZ-2208 (above, manufactured by Toray Dow Corning Co., Ltd.), KF-353, KF-615A, KF-640, KF-642, KF-643, KF-6020, X-22-6191, KF-60 1, KF-6015, X-22-2516, KF-410, X-22-821, KF-412, KF-413, KF-4701 (manufactured by Shin-Etsu Chemical Co.) and the like.

(Fluorine compound)
Examples of the fluorine compound include fluorine-based resins having a perfluoroalkyl group or a perfluoroalkenyl group in the molecule. Commercially available products include, for example, MegaFuck F-444, F-472, F-477, F-552, F-553, F-554, F-443, F-470, F- 470, F-475, F-482, F-482, F-487, F-487, R-30, RS-75 (manufactured by DIC Corporation), F-top EF301, 303, 352 (Shin-Akita Kasei Co., Ltd.), Florad FC-430, FC-431 (Sumitomo 3M Co., Ltd.), Asahi Guard AG-E300D, Surflon S-382, SC-101, SC- 102, SC-103, SC-104, SC-105, SC-106 (above, Asahi Glass Co., Ltd.), BM-1000, BM-1100 (above, Yusho Co., Ltd.), NBX -15, FTX-218 (above, (Manufactured by Neos Co., Ltd.).

The amount of one or both of the silicone compound and fluorine compound used in the present invention is preferably 0.01 to 20 parts by mass, more preferably 0.01 to 100 parts by mass of the binder component. To 10 parts by mass, more preferably 0.05 to 3 parts by mass. When the blending amount of either one or both of the silicone compound and the fluorine compound is 0.01% by mass or more, the desired effect of the present invention can be obtained satisfactorily. On the other hand, in the case of 20 mass% or less, film forming property improves.

Furthermore, the printed wiring board material of the present invention preferably contains cellulose fibers having a number average fiber diameter of 1 μm or more and cellulose nanofibers having the number average fiber diameter of 3 nm or more and less than 1000 nm. By combining and blending cellulose fibers having different fiber diameters, it is possible to realize a high peel strength as compared with the conventional case.

(Cellulose fiber)
The cellulose fiber can be obtained as follows.
Examples of the raw material of the cellulose fiber include the same materials as the cellulose nanofiber.

In order to produce cellulose fibers from the above raw materials, a method of beating or crushing the above raw materials can be used.

In the above beating or pulverization treatment, for example, pulp is mechanically treated with a high-pressure homogenizer or the like to loosen the fiber to a fiber diameter of about 1 to 10 μm, and the cellulose fiber is made into a water suspension of about 0.1 to 3% by mass. Obtainable.

For example, cellulose nanofibers having a fiber diameter of about 10 to 100 nm can also be obtained by repeatedly unraveling cellulose fibers obtained by beating or pulverization with a grinder or the like.

In addition, the cellulose fiber used in the present invention may be one having enhanced functionality by chemical modification and / or physical modification in the same manner as the cellulose nanofiber.

The number average fiber diameter of the cellulose fiber used in the present invention is a value obtained in the same manner as the cellulose nanofiber.

The number average fiber diameter of the cellulose fibers needs to be 1 μm or more, preferably 1 μm to 50 μm, more preferably 1 μm to 20 μm. If the number average fiber diameter of the cellulose fiber is smaller than the above range, the desired effect cannot be obtained.

In the present invention, in the preparation process of the cellulose nanofibers, when unraveling the fibers to nano size, the treatment is stopped in the middle and the whole amount is not unraveled, leaving the cellulose fibers in the range of the number average fiber diameter. Also, a mixture of cellulose fiber and cellulose nanofiber satisfying the preferred conditions of the present invention can be obtained. Therefore, the printed wiring board material of the present invention has a number average fiber diameter outside the range of the specific number average fiber diameter in addition to the cellulose fiber and the cellulose nanofiber satisfying the specific number average fiber diameter range. Cellulose fibers may be included.

As the cellulose fiber, a commercially available product can be appropriately used as long as it satisfies the condition of the number average fiber diameter, and is not particularly limited.

According to the present invention, an excellent peel strength can be realized by combining the cellulose fiber and the cellulose nanofiber in combination. In the present invention, the mass ratio of the cellulose fiber to the cellulose nanofiber is preferably 9: 1 to 1: 9, more preferably 8: 2 to 2: 8. By setting it within this range, higher peel strength can be obtained.

In this case, the total amount of the cellulose fiber and the cellulose nanofiber is preferably 0.5 to 80% by mass, more preferably 1 to 70% by mass with respect to the total amount of the composition excluding the solvent. is there. By making the total amount of the cellulose fibers and the cellulose nanofibers 0.5% by mass or more, higher peel strength can be obtained, and by 80% by mass or less, good film-forming properties are obtained. Can be obtained.

Furthermore, the printed wiring board material of the present invention preferably contains cellulose nanofibers having a carboxylate in the structure and a number average fiber diameter of 3 nm to 1000 nm. Thereby, the printed wiring board material excellent in crack resistance can be obtained. Such cellulose nanofibers can be obtained by oxidizing natural cellulose fibers and then refining them according to the following.

(Cellulose nanofibers with carboxylate in the structure)
First, an aqueous dispersion is prepared by dispersing natural cellulose fibers in about 10 to 1000 times (mass basis) of water on an absolute dry basis using a mixer or the like. Examples of the natural cellulose fiber used as a raw material for the cellulose nanofiber include wood pulp such as softwood pulp and hardwood pulp, non-wood pulp such as straw pulp and bagasse pulp, cotton pulp such as cotton lint and cotton linter, Examples include bacterial cellulose. These may be used individually by 1 type, or may be used in combination of 2 or more types as appropriate. Further, these natural cellulose fibers may be subjected to a treatment such as beating in order to increase the surface area in advance.

Next, natural cellulose fibers are oxidized in the aqueous dispersion using an N-oxyl compound as an oxidation catalyst. Examples of such N-oxyl compounds include TEMPO (2,2,6,6-tetramethylpiperidine-N-oxyl), 4-carboxy-TEMPO, 4-acetamido-TEMPO, 4-amino-TEMPO, 4 -Dimethylamino-TEMPO, 4-phosphonooxy-TEMPO, 4-hydroxy TEMPO, 4-oxy TEMPO, 4-methoxy TEMPO, 4- (2-bromoacetamido) -TEMPO, 2-azaadamantane N-oxyl, etc. TEMPO derivatives having various functional groups at the C4 position can be used. As the addition amount of these N-oxyl compounds, a catalytic amount is sufficient, and it can usually be in a range of 0.1 to 10% by mass with respect to natural cellulose fiber on an absolute dry basis.

In the oxidation treatment of the natural cellulose fiber, an oxidizing agent and a co-oxidizing agent are used in combination. Examples of the oxidizing agent include halous acid, hypohalous acid and perhalogenic acid and salts thereof, hydrogen peroxide, perorganic acid, among which sodium hypochlorite and sodium hypobromite. Alkali metal hypohalites such as are preferred. Further, as the co-oxidant, for example, an alkali metal bromide such as sodium bromide can be used. The amount of the oxidizing agent used is usually in the range of about 1 to 100% by mass based on the absolute dry standard relative to the natural cellulose fiber, and the amount of the co-oxidant used is usually based on the absolute dry standard relative to the natural cellulose fiber Is about 1 to 30% by mass.

In the oxidation treatment of the natural cellulose fiber, it is preferable to maintain the pH of the aqueous dispersion in the range of 9 to 12 from the viewpoint of efficiently proceeding the oxidation reaction. In addition, the temperature of the aqueous dispersion during the oxidation treatment can be arbitrarily set in the range of 1 to 50 ° C., and the reaction can be performed at room temperature without temperature control. The reaction time can be in the range of 1 to 240 minutes. In addition, a penetrant can be added to the aqueous dispersion in order to allow the drug to penetrate into the inside of the natural cellulose fiber and introduce more carboxyl groups into the fiber surface. Examples of the penetrating agent include anionic surfactants such as carboxylate, sulfate ester salt, sulfonate salt, and phosphate ester salt, and nonionic surfactants such as polyethylene glycol type and polyhydric alcohol type. .

After the oxidation treatment of the natural cellulose fiber, it is preferable to carry out a purification treatment to remove impurities such as unreacted oxidant and various by-products contained in the aqueous dispersion prior to refinement. Specifically, for example, a technique of repeatedly washing and filtering the oxidized natural cellulose fiber can be used. The natural cellulose fiber obtained after the refining treatment is usually subjected to a refining treatment in a state impregnated with an appropriate amount of water. However, if necessary, the natural cellulose fiber may be dried to obtain a fibrous or powdery form.

Next, the refinement of the natural cellulose treatment is performed in a state where the natural cellulose fibers purified as desired are dispersed in a solvent such as water. The solvent as a dispersion medium used in the micronization treatment is usually preferably water, but if desired, alcohols (methanol, ethanol, isopropanol, isobutanol, sec-butanol, tert-butanol, methyl cellosolve, ethyl cellosolve, Ethylene glycol, glycerin, etc.), ethers (ethylene glycol dimethyl ether, 1,4-dioxane, tetrahydrofuran, etc.), ketones (acetone, methyl ethyl ketone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, etc.), etc. A water-soluble organic solvent may be used, or a mixture thereof may be used. The solid content concentration of the natural cellulose fiber in the dispersion of these solvents is preferably 50% by mass or less. When the solid content concentration of the natural cellulose fiber exceeds 50% by mass, extremely high energy is required for dispersion, which is not preferable. Refinement of natural cellulose treatment includes low-pressure homogenizers, high-pressure homogenizers, grinders, cutter mills, ball mills, jet mills, beating machines, disintegrators, short-screw extruders, twin-screw extruders, ultrasonic agitators, household juicer mixers, etc. This can be done using a dispersing device.

The cellulose nanofibers obtained by the refinement treatment can be made into a suspension in which the solid content concentration is adjusted, or a dried powder, as desired. Here, in the case of a suspension, only water may be used as a dispersion medium, and water and other organic solvents, for example, alcohols such as ethanol, surfactants, acids, bases, etc. A mixed solvent may be used.

By the oxidation treatment and refinement treatment of the natural cellulose fiber, the hydroxyl group at the C6 position of the structural unit of the cellulose molecule is selectively oxidized to a carboxyl group via an aldehyde group, and the content of the carboxyl group is 0.1. A highly crystalline cellulose nanofiber having the above-mentioned predetermined number average fiber diameter, which is composed of cellulose molecules of ˜3 mmol / g, can be obtained. This highly crystalline cellulose nanofiber has a cellulose I-type crystal structure. This means that the cellulose nanofibers are those obtained by surface-oxidizing naturally-derived cellulose molecules having an I-type crystal structure. That is, natural cellulose fibers have a high-order solid structure formed by a bundle of fine fibers called microfibrils produced in the process of biosynthesis, and a strong cohesive force between the microfibrils (between surfaces). The cellulose nanofibers can be obtained by weakening the hydrogen bond) by introducing an aldehyde group or a carboxyl group by an oxidation treatment, and further through a refinement treatment. By adjusting the conditions of the oxidation treatment, the content of the carboxyl group is increased or decreased, the polarity is changed, or by the electrostatic repulsion or refinement treatment of the carboxyl group, the average fiber diameter or average fiber length of the cellulose nanofiber, The average aspect ratio can be controlled.

That the natural cellulose fiber has a type I crystal structure is typical at two positions in the vicinity of 2θ = 14 to 17 ° and 2θ = 22 to 23 ° in a diffraction profile obtained by measurement of a wide-angle X-ray diffraction image. It can be identified from having a typical peak. In addition, the introduction of a carboxyl group into the cellulose molecule of the cellulose nanofibers indicates that in a sample from which moisture has been completely removed, absorption due to a carbonyl group (1608 cm ⁻¹ ) in the total reflection infrared spectroscopic spectrum (ATR). This can be confirmed by the presence of the vicinity. In the case of a carboxyl group (COOH), there is an absorption at 1730 cm ⁻¹ in the above measurement.

In addition, since halogen atoms are attached or bonded to the natural cellulose fiber after the oxidation treatment, dehalogenation treatment can be performed for the purpose of removing such residual halogen atoms. The dehalogenation treatment can be performed by immersing the oxidized natural cellulose fiber in a hydrogen peroxide solution or an ozone solution.

Specifically, for example, the oxidized natural cellulose fiber is added to a hydrogen peroxide solution having a concentration of 0.1 to 100 g / L in a bath ratio of about 1: 5 to 1: 100, preferably 1:10 to 1. : Immerse under conditions of about 60 (mass ratio). In this case, the concentration of the hydrogen peroxide solution is preferably 1 to 50 g / L, and more preferably 5 to 20 g / L. The pH of the hydrogen peroxide solution is preferably 8 to 11, more preferably 9.5 to 10.7.

The amount [mmol / g] of carboxyl groups in cellulose relative to the weight of cellulose nanofibers contained in the aqueous dispersion can be evaluated by the following method. That is, 60 ml of a 0.5 to 1% by mass aqueous dispersion of a cellulose nanofiber sample, the dry weight of which was precisely weighed in advance, was prepared, and the pH was adjusted to about 2.5 with 0.1 M hydrochloric acid aqueous solution. An aqueous sodium hydroxide solution is dropped until the pH is about 11, and the electrical conductivity is measured. From the amount (V) of sodium hydroxide consumed in the weak acid neutralization stage where the change in electrical conductivity is slow, the functional group amount can be determined using the following formula. This amount of functional groups indicates the amount of carboxyl groups.
Functional group amount [mmol / g] = V [ml] × 0.05 / cellulose nanofiber sample [g]

The number average fiber diameter of the cellulose nanofiber having a carboxylate salt in the structure used in the present invention can be the same as that of the cellulose nanofiber.

In this case, the amount of the cellulose nanofiber having a carboxylate in the structure in the printed wiring board material is preferably 0.1 to 80% by mass, more preferably based on the total amount of the composition excluding the solvent. Is 0.2 to 70% by mass. When the blending amount of the cellulose nanofiber having a carboxylate salt in the structure is 0.1% by mass or more, the desired effect of the present invention can be obtained satisfactorily. On the other hand, in the case of 80 mass% or less, film forming property improves.

Furthermore, the printed wiring board material of the present invention preferably contains cellulose nanofibers (hereinafter also referred to as lignocellulose nanofibers) produced from lignocellulose and having a number average fiber diameter of 3 nm to 1000 nm. Thereby, this cellulose nanofiber can be obtained as follows. In a high-definition circuit or a large current application, a printed wiring board material that has a high withstand voltage between circuits and can maintain high insulation reliability over a long period of time can be obtained.

(Lignocellulose nanofiber)
Lignocellulose that exists in nature has a three-dimensional network hierarchical structure in which cellulose is tightly bound to lignin and hemicellulose. Cellulose molecules in the cell wall are not single molecules but regularly agglomerate to collect dozens of them. Crystalline microfibrils (cellulose nanofibers) are formed. Specifically, the lignocellulose used in the present invention can be obtained from, for example, woody biomass obtained from plants such as wood, agricultural products, vegetation, and cotton, or bacterial cellulose produced by microorganisms. In order to produce cellulose nanofibers from lignocellulose, a method of mechanically grinding in the presence of a medium can be used.

Such mechanical pulverization methods include, for example, a ball mill (vibrating ball mill, rotating ball mill, planetary ball mill), rod mill, bead mill, disk mill, cutter mill, hammer mill, impeller mill, extruder, mixer (high-speed rotating blade mixer, Homogenizer), homogenizer (high pressure homogenizer, mechanical homogenizer, ultrasonic homogenizer) and the like. Among these, pulverization is preferably performed by a ball mill, a rod mill, a bead mill, a disk mill, a cutter mill, an extruder or a mixer. By using these pulverization methods, cellulose nanofibers can be produced relatively easily. Moreover, the size variation of the cellulose nanofiber obtained becomes small.

The medium used in the pulverization step is not particularly limited, but water, a low molecular compound, a high molecular compound, fatty acids, and the like are preferably used. These may be used alone or in combination of two or more. Among these, it is preferable to mix water and a low molecular compound, a high molecular compound, or fatty acids, and to use as a pulverization medium.

Among these, examples of the low molecular weight compound include alcohols, ethers, ketones, sulfoxides, amides, amines, aromatics, morpholines, ionic liquids, and the like. Examples of the polymer compound include alcohol polymers, ether polymers, amide polymers, amine polymers, aromatic polymers, and the like. Furthermore, examples of fatty acids include saturated fatty acids and unsaturated fatty acids. In this case, it is preferable to use water-soluble compounds as the low molecular compounds, polymer compounds and fatty acids to be used.

Further, prior to the pulverization step, ozone treatment as a pretreatment may be performed in order to facilitate pulverization.

The number average fiber diameter of the lignocellulose nanofiber used in the present invention can be the same as that of the cellulose nanofiber.

In this case, the amount of the above lignocellulose nanofibers in the printed wiring board material is preferably 0.1 to 80% by mass, more preferably 0, based on the total amount of the composition excluding the organic solvent described later. 2 to 70% by mass. When the blending amount of the cellulose nanofiber is 0.1% by mass or more, the desired effect of the present invention can be obtained satisfactorily. On the other hand, in the case of 80 mass% or less, film forming property improves.

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 Corp., trade name: Cyclomer A200), 3. dimethylbenzylamine as a ring-opening catalyst; 6 g and 1.80 g of hydroquinone monomethyl ether as a polymerization inhibitor were added, 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.

Further, tetrahydrophthalic anhydride was added to the OH group of the resin obtained above at 95 to 105 ° C. for 8 hours at a molar ratio of 0.26. 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, stirrer, dropping funnel and 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. After 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 (BiNFi-s (binfis) 10% by weight cellulose, number average fiber diameter 80 nm, manufactured by Sugino Machine Co., Ltd.) was dehydrated and filtered, and 10 times the amount of carbitol acetate as the weight of the filtrate was added, followed by stirring for 30 minutes. And then 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.

* 1-1) Thermosetting compound 1: Epicote 828, manufactured by Mitsubishi Chemical Corporation * 1-2) Thermosetting compound 2: Epicote 807, manufactured by Mitsubishi Chemical Corporation * 1-3) Curing catalyst 1: 2MZ-A Shikoku Kasei Kogyo Co., Ltd. * 1-4) Acrylic copolymer compound 1: BYK-361N Bicchem Japan Co., Ltd. * 1-5) Acrylic copolymer compound 2: Polyflow No. 50EHF (solid content 50% by mass) * 1-6) Acrylic copolymer compound 3 manufactured by Enomoto Kasei Co., Ltd. 90 manufactured by Enomoto Kasei Co., Ltd. * 1-7) Colorant: Phthalocyanine Blue * 1-8) Organic solvent: Carbitol acetate

* 1-9) Thermosetting compound 3: Unidic V-8000 (solid content: 40% by mass), manufactured by DIC Corporation * 1-10) Thermosetting compound 4: Denacol EX-830, manufactured by Nagase ChemteX Corporation * 1-11) Curing catalyst 2: Triphenylphosphine * 1-12) Photocurable compound 1: Bisphenol A type epoxy acrylate * 1-13) Photocurable compound 2: Trimethylolpropane triacrylate * 1-14) Photocurable compound 3: Kayamar PM2 Nippon Kayaku Co., Ltd. * 1-15) Photocurable compound 4: Light ester HO Kyoeisha Chemical Co., Ltd. * 1-16) Photopolymerization initiator 1 : 2-ethylanthraquinone

* 1-17) Thermoplastic resin 1: Novatec PP BC03L manufactured by Nippon Polypro Co., Ltd. * 1-18) Thermoplastic resin 2: Novatec LD LC561 manufactured by Nippon Polyethylene Co., Ltd.

* 1-19) Thermoplastic resin 3: Socsea SOXR-OB, varnish manufactured by Nippon Kogyo Paper Industries Co., Ltd. (solid content 70% by mass, N-methylpyrrolidone 30% by mass)

[Preparation of composition]
Examples 1-1 to 1-12 and Comparative Examples 1-1 to 1-3 in Table 1 and Table 2, and Examples 1-19 to 1-21 in Table 4 above For Comparative Example 1-6, each component was blended, stirred, and dispersed with a three roll to prepare compositions.

[Production of composite molded body]
For Examples 1-13 to 1-15 and Comparative Example 1-4 in Table 3 above, each component was blended and then 180 ° C. using a kneader (Laboplast Mill, manufactured by Toyo Seiki Co., Ltd.). For 10 minutes at a rotational speed of 70 rpm. 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., 0 Cooled and pressed at 5 MPa for 1 minute. Thereby, a sheet-like cellulose nanofiber composite molded body having a thickness of 0.05 mm was obtained.

For Examples 1-16 to 1-18 and Comparative Example 1-5 in Table 3 above, each component was blended and then 150 ° C. using a kneader (labor plast mill, manufactured by Toyo Seiki Co., Ltd.). For 10 minutes at a rotational speed of 70 rpm. 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., 0 Cooled and pressed at 5 MPa for 1 minute. Thereby, a sheet-like cellulose nanofiber composite molded body having a thickness of 0.05 mm was obtained.

(Preparation of smear removability evaluation test piece)
FIG. 2 is an explanatory view showing a method for producing a smear removability evaluation substrate. In the figure, (a) to (c-1) are plan views, and (c-2) is a sectional view of (c-1). As shown in FIG. 2, the compositions of Examples 1-1 to 1-6 and Comparative Example 1-1 were measured in a thickness of 50 mm × 50 mm in which a conductor layer 13a was provided on an insulating layer 13b. 1.6mm thick FR-4 copper-clad laminate (with copper pad, copper thickness 18μm), printed on the entire surface by screen printing method, 140 ° C for 30 minutes in a hot air circulation drying oven The insulating resin layer 14 was formed by curing. Next, a hole (via) 15 having a diameter of 100 μm was formed on the conductor layer 13a with a carbon dioxide gas laser to produce a test piece.

The compositions of Examples 1-7 to 1-9 and Comparative Example 1-2 were printed on the entire surface of the test substrate by the screen printing method, and the conditions were 100 ° C. for 30 minutes in a hot air circulating drying furnace. After drying, a test piece was prepared in the same manner as above except that it was cured at 170 ° C. for 60 minutes to form an insulating resin layer.

The compositions of Examples 1-10 to 1-12 and Comparative Example 1-3 were printed on the entire surface of the test substrate by a screen printing method, and ² J / cm ² at a wavelength of 350 nm using a metal halide lamp. A test piece was prepared in the same manner as described above except that the integrated light amount was irradiated and cured to form an insulating resin layer.

The cellulose nanofiber composite molded bodies having a thickness of 0.05 mm of Examples 1-13 to 1-18, Comparative Examples 1-4, and Comparative Examples 1-5 were placed on the test substrate at 190 ° C. and 20 MPa for 1 minute. A test piece was prepared in the same manner as described above except that the insulating resin layer was formed by further hot pressing for 23 minutes at 25 ° C. and 0.5 MPa for 1 minute.

The compositions of Examples 1-19 to 1-21 and Comparative Example 1-6 were printed on the entire surface of the above test substrate by the screen printing method, and the conditions were 120 ° C. and 10 minutes in a hot air circulating drying oven. After drying, a test piece was prepared in the same manner as above except that it was cured at 250 ° C. for 30 minutes to form an insulating resin layer.

(Smear removal)
Each test piece was immersed in a mixed solution of Circposit MLB Conditioner 211 (Rohm and Haas, 200 ml / l) and Circposit Z (Rohm and Haas, 100 ml / l) as a swelling liquid at 80 ° C. for 5 minutes. Next, as a roughening solution, a mixture of Circposit MLB promoter 213A (Rohm and Haas, 100 ml / l) and Circposit MLB promoter 213B (Rohm and Haas, 150 ml / l) was added at 80 ° C. for 10 minutes. Finally, it was immersed in a circular deposit MLB neutralizer 216-2 (Rohm and Haas, 200 ml / l) as a neutralizing solution at 50 ° C. for 5 minutes. Thereafter, the via bottom (copper surface) was observed with a scanning electron microscope (SEM, JSM-6610LV, JEOL Ltd., magnification: 3,500 times), and the presence of smear on the via bottom (copper surface) was visually confirmed. did. The evaluation criteria are as follows. The evaluation results are shown in Table 5 and Table 6 below.
(Evaluation) ○: No smear ×: With smear

(Preparation of heat resistance, acid resistance and pencil hardness test specimens)
Each test piece was produced by forming an insulating resin layer on a test substrate of FR-4 copper-clad laminate (copper thickness 18 μm) having a size of 50 mm × 50 mm and a thickness of 1.6 mm. The insulating resin layer was formed under the same conditions as described for the smear removability evaluation test piece.

(Heat-resistant)
After applying rosin-based flux using each of the above test pieces, it was allowed to flow in a solder bath set at 260 ° C. for 30 seconds in advance, washed with propylene glycol monomethyl ether acetate, dried, and then peel-tested with a cellophane adhesive tape. It was performed and the presence or absence of peeling of the coating film was confirmed. The evaluation criteria are as follows. The evaluation results are shown in Table 5 and Table 6 below.
(Evaluation) ○: The coating film has no peeling ×: The coating film has peeling

(Acid resistance)
Each test piece was immersed in a 10% by volume sulfuric acid aqueous solution at 25 ° C. for 60 minutes, washed with water, and dried. Thereafter, a peel test with a cellophane adhesive tape was performed to confirm the presence or absence of peeling of the coating film. Evaluation criteria are the same as the above heat resistance. The evaluation results are shown in Table 5 and Table 6 below.

(Pencil hardness)
Using each of the above test pieces, the pencil of B to 9H sharpened so that the tip of the core becomes flat is pressed at an angle of about 45 °, and the pencil hardness that does not cause peeling of the coating film is obtained. Recorded. The results are shown in Table 5 and Table 6 below.

(Preparation of electrical insulation test piece)
Using an FR-4 copper-clad laminate (copper thickness 18 μm) with a size of 100 mm × 150 mm and a thickness of 1.6 mm, an IPC standard B pattern comb-shaped electrode pattern was prepared by an etching method, did. Each test piece was produced by forming an insulating resin layer on the test substrate so as to cover the comb-shaped electrode portion. The insulating resin layer was formed under the same conditions as described for the smear removability evaluation test piece.

(Electrical insulation)
Using each of the above test pieces, a bias of 500 V DC was applied between the comb electrodes, and the insulation resistance value was measured. When the value was 100 GΩ or more, it was rated as “◯”, and when it was less than 100 GΩ, it was marked as “X”. The results are shown in Table 5 and Table 6 below.

(Preparation of test piece for evaluating peel strength of plating layer)
An insulating resin layer was formed on a test substrate of FR-4 copper-clad laminate (copper thickness: 18 μm) having a size of 50 mm × 50 mm and a thickness of 1.6 mm. The insulating resin layer was formed under the same conditions as described for the smear removability evaluation test piece. Next, each test piece was produced by forming a plating layer on the entire surface of the insulating resin layer by an electroless copper plating method and then an electrolytic copper plating method.

(Peeling strength test for plating layer (peel strength test))
A notch with a width of 10 mm and a length of 100 mm was cut into the plating layer of each test piece, and one end was peeled off and grasped with a gripper, and 35 mm was peeled off at a rate of 50 mm / min in the vertical direction at room temperature. The load at the time was measured. If it was 0.8 kN / m or more, it was rated as ◯, and if it was less than 0.8 kN / m, it was marked as x. The results are shown in Table 5 and Table 6 below.

As described above in detail, according to the printed wiring board material of the present invention, it can be seen that smear on the surface of a metal foil such as copper is difficult to occur and is easy to remove even if it occurs. Moreover, it was confirmed that the printed wiring board material of the present invention has sufficient characteristics as a solder resist and an interlayer insulating material.

<Example 2>
[Production of evaluation sheet]
In accordance with the description in Table 7 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 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 7.

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

According to the description in Table 8 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, 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.

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

According to the description in Table 9 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.). 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.

* 2-10) Thermoplastic resin 1: Novatec PP BC03L manufactured by Nippon Polypro Co., Ltd.

According to the description in Table 10 below, each component was blended 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.

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

According to the description in Table 11 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, 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.

* 2-12) 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 12 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.

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

In accordance with the description in Table 13 to Table 15 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 that can cover 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.

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

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

* 3-1) Thermosetting compound 1: Epicoat 828, manufactured by Mitsubishi Chemical Corporation * 3-3) Thermosetting compound 2: Epicoat 807, manufactured by Mitsubishi Chemical Corporation * 3-3) Curing catalyst 1: 2MZ-A * 3-4) Colorant: Phthalocyanine Blue * 3-5) Silicone compound 1: BYK-313 (solid content 15% by mass) * 3-6) Silicone compound manufactured by Big Chemie Japan Co., Ltd. 2: SH-8400 manufactured by Toray Dow Corning Co., Ltd. * 3-7) Silicone compound 3: KS-66 manufactured by Shin-Etsu Chemical Co., Ltd. * 3-8) Fluorine compound 1: Megafac RS-75 (solid content 40 mass) %) DIC Corporation * 3-9) Fluorine Compound 2: Asahi Guard AG-E300D (solid content 30% by mass) Asahi Glass Co., Ltd. * 3-10) Organic Solvent: Carbitol Acetate

* 3-11) Thermosetting compound 3: Unidic V-8000 (solid content 40% by mass) manufactured by DIC Corporation * 3-12) Thermosetting compound 4: Denacol EX-830 manufactured by Nagase ChemteX Corporation * 3-13) Thermosetting compound 5: TEPIC-H, Nissan Chemical Co., Ltd. * 3-14) Thermoplastic resin 1: Novatec PPBC03L, Nippon Polypro Co., Ltd. * 3-15) Thermoplastic resin 2: Novatec LDLC561 * 3-16) Thermoplastic resin 3 manufactured by Nippon Polyethylene Co., Ltd .: Socsea SOXR-OB (solid content 70% by mass) Varnish manufactured by Nippon Kogyo Paper Industries Co., Ltd. * 3-17) Photo-curable compound 1: Bisphenol A Type epoxy acrylate manufactured by Mitsubishi Chemical Co., Ltd. * 3-18) Photocurable compound 2: Trimethylolpropane triacrylate * 3-19) Photocurable compound 3: Kayamer PM2 Nippon Kayaku Co., Ltd. * 3-20) Photocurable Compound 4: Light Ester HO Kyoeisha Chemical Co., Ltd. * 3-21) Photocurable Compound 5: Dipentaerythritol Tetraacrylate * 3-22 ) Curing catalyst 2: Triphenylphosphine * 3-23) Curing catalyst 3: Finely ground melamine * 3-24) Curing catalyst 4: Dicyandiamide * 3-25) Photopolymerization initiator 1: 2-ethyl Anthraquinone * 3-26) Photopolymerization initiator 2: Irgacure 907 manufactured by BASF

Each component was blended according to the blending in the above table (excluding Example 3-14, Example 3-15, Example 3-22, Example 3-23, Comparative Example 3-3 and Comparative Example 3-4) The mixture was stirred and dispersed with three rolls to prepare compositions. In addition, the number in a table | surface shows a mass part.

For Example 3-14, Example 3-22, and Comparative Example 3-3, the respective components were blended and used at 180 ° C. for 10 minutes using a kneader (laboplast mill, manufactured by Toyo Seiki Co., Ltd.) Melt kneading was performed at a rotation speed of 70 rpm. 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., 0 Cooled and pressed at 5 MPa for 1 minute. This obtained the sheet-like cellulose nanofiber composite molded object of thickness 0.5mm and 0.05mm.

For Example 3-15, Example 3-23, and Comparative Example 3-4, the respective components were blended and used at 150 ° C. for 10 minutes using a kneader (laboplast mill, manufactured by Toyo Seiki Co., Ltd.) Melt kneading was performed at a rotation speed of 70 rpm. 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., 0 Cooled and pressed at 5 MPa for 1 minute. This obtained the sheet-like cellulose nanofiber composite molded object of thickness 0.5mm and 0.05mm.

[Evaluation as interlayer insulation material]
(Preparation of test piece)
FIG. 3 is an explanatory view showing a method for producing a substrate for evaluating an interlayer insulating material. In the figure, (a) to (e-1) are plan views, and (e-2) is a sectional view of (e-1). As shown in FIG. 3, the compositions of Examples 3-1 to 3-12 and Comparative Example 3-1 were 50 mm × 50 mm in thickness with the conductor layer 21a provided on the insulating layer 21b. Printed on the entire surface of a test substrate 21 of a 1.6 mm thick FR-4 copper-clad laminate (with copper pad, copper thickness 18 μm) by screen printing method, at 140 ° C. for 30 minutes in a hot air circulating drying oven The insulating resin layer 22 was formed by curing. Next, a hole (via) 23 having a diameter of 100 μm is formed on the conductor layer 21a with a carbon dioxide laser, and then smear is removed with an aqueous potassium permanganate solution, followed by electroless copper plating and then electrolytic copper plating on the entire surface. Thus, the plating layer 24 was formed. Furthermore, the test piece was produced by forming the wiring pattern 26 by the etching method. Reference numeral 25 in the figure indicates an etching resist pattern.

The compositions of Example 3-13, Example 3-21 and Comparative Example 3-2 were printed on the entire surface of the above test substrate by screen printing, and the conditions were 100 ° C. and 30 minutes in a hot air circulating drying oven. And dried at 170 ° C. for 60 minutes. Next, a test piece was prepared by forming a wiring pattern in the same manner as described above.

Sheet-like cellulose nanofiber having a thickness of 0.05 mm comprising Example 3-14, Example 3-15, Example 3-22, Example 3-23, Comparative Example 3-3, and Comparative Example 3-4 The composite molded body was hot-pressed on the test substrate at 190 ° C. and 20 MPa for 1 minute, and further cold-pressed at 23 ° C. and 0.5 MPa for 1 minute. Next, a test piece was prepared by forming a wiring pattern in the same manner as described above.

The compositions of Example 3-16, Example 3-24, and Comparative Example 3-5 were printed on the entire surface of the test substrate by the screen printing method, and were heated at 120 ° C. for 10 minutes in a hot air circulating drying oven. After drying, it was cured at 250 ° C. for 30 minutes. Next, a test piece was prepared by forming a wiring pattern in the same manner as described above.

The compositions of Example 3-17, Example 3-25, and Comparative Example 3-6 were printed on the entire surface of the test substrate by a screen printing method, and accumulated at ² J / cm ² at a wavelength of 350 nm using a metal halide lamp. Light was irradiated and cured. Next, a test piece was prepared by forming a wiring pattern in the same manner as described above.

The compositions of Example 3-18 to Example 3-20, Example 3-26 to Example 3-28 and Comparative Example 3-7 to Comparative Example 3-9 were printed on the entire surface by screen printing. Then, it was dried in a hot air circulation drying oven at 80 ° C. for 30 minutes. Next, using a negative pattern that can cover 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. A developing solution for a printed wiring board was used for 60 seconds by using a sodium carbonate aqueous solution as a developing solution, and the edges were then thermally cured at 150 ° C. for 60 minutes in a hot air circulating drying oven. Next, a test piece was prepared by forming a wiring pattern in the same manner as described above.

(Insulation reliability evaluation)
A direct voltage of 50 V was applied to the electrodes of the six test pieces, and a standing test was performed in an atmosphere of 130 ° C. and 85%. The insulation resistance was measured in the test tank, and the time when it became 1/100 from the insulation resistance value 1 hour after the start of the test was recorded. If the insulation resistance value did not decrease after 100 hours, it was terminated. The results are shown in the table below.

[Evaluation as core material]
(Production of cellulose nanofiber sheet)
About cellulose nanofiber, 0.2 mass% water suspension was produced with distilled water, it filtered with the glass filter, and it formed into a film, and produced the sheet | seat of the size of 50 mm x 50 mm and thickness 40 micrometers.

(Example 3-29)
50 parts by mass of Epicoat 828 manufactured by Mitsubishi Chemical Corporation, 50 parts by mass of Epicoat 807 manufactured by Mitsubishi Chemical Corporation, 1 part by mass of an acrylic copolymer (BYK-361N manufactured by BYK Chemie Japan Co., Ltd.), Shikoku 3 parts by mass of 2MZ-A manufactured by Kasei Kogyo Co., Ltd., 2 parts by mass of BYK-313 manufactured by Big Chemie Japan Co., Ltd., and 100 parts by mass of methyl ethyl ketone were mixed and stirred to prepare a resin solution. This was impregnated into each cellulose nanofiber sheet, left in an atmosphere at 50 ° C. for 12 hours, then taken out and dried at 80 ° C. for 5 hours to prepare a prepreg. Ten prepregs were stacked, and a copper foil having a thickness of 18 μm was stacked on the front and back, and cured for 3 hours in a vacuum press at a temperature of 160 ° C. and a pressure of 2 MPa. Next, as shown in FIGS. 4A to 4C, a through hole 27 having a drill diameter of 300 μm is formed by drilling on the laminated plate 21 made of the insulating layer 21b having the conductor layer 21a formed on both surfaces thereof. , With a pitch of 5 mm. Thereafter, smear was removed with an aqueous potassium permanganate solution, electroless copper plating treatment, and then electrolytic copper plating treatment were performed to form through holes 28. Next, as shown in FIGS. 5A to 5C, a wiring pattern 26 was produced by an etching method to obtain a test piece.

(Example 3-30)
50 parts by mass of Epicoat 828 manufactured by Mitsubishi Chemical Corporation, 50 parts by mass of Epicoat 807 manufactured by Mitsubishi Chemical Corporation, 1 part by mass of an acrylic copolymer (BYK-361N manufactured by BYK Chemie Japan Co., Ltd.), Shikoku 3 parts by mass of 2MZ-A manufactured by Kasei Kogyo Co., Ltd., 0.75 parts by mass of MegaFac RS-75 manufactured by DIC Co., Ltd., and 100 parts by mass of methyl ethyl ketone are mixed and stirred to prepare a resin solution. A test piece was obtained in the same manner as in Example 3-29 except for the above.

(Comparative Example 3-10)
50 parts by mass of Epicoat 828 manufactured by Mitsubishi Chemical Corporation, 50 parts by mass of Epicoat 807 manufactured by Mitsubishi Chemical Corporation, 3 parts by mass of 2MZ-A manufactured by Shikoku Chemicals Co., Ltd., and 100 parts by mass of methyl ethyl ketone A test piece was obtained in the same manner as in Example 3-29 except that a resin solution was prepared by mixing a part.

(Example 3-31)
100 parts by weight of Unidic V-8000 manufactured by DIC Corporation, 23 parts by weight of Denacol EX-830 manufactured by Nagase ChemteX Corporation, acrylic copolymer (BYK-361N manufactured by BYK Japan Japan Co., Ltd.) 1 part by weight, 1 part by weight of triphenylphosphine, 2 parts by weight of BYK-313 manufactured by Big Chemie Japan Co., Ltd., and 100 parts by weight of methyl ethyl ketone were mixed, and the procedure was carried out except that a resin solution was prepared. A test piece was obtained in the same manner as in Example 3-29.

(Example 3-32)
100 parts by weight of Unidic V-8000 manufactured by DIC Corporation, 23 parts by weight of Denacol EX-830 manufactured by Nagase ChemteX Corporation, acrylic copolymer (BYK-361N manufactured by BYK Japan Japan Co., Ltd.) 1 part by weight, 1 part by weight of triphenylphosphine, 0.75 part by weight of Megafic RS-75 manufactured by DIC Corporation, and 100 parts by weight of methyl ethyl ketone were mixed and stirred to produce a resin solution Obtained a test piece in the same manner as in Example 3-29.

(Comparative Example 3-11)
100 parts by weight of Unidic V-8000 manufactured by DIC Corporation, 23 parts by weight of Denacol EX-830 manufactured by Nagase ChemteX Corporation, 1 part by weight of triphenylphosphine, and 100 parts by weight of methyl ethyl ketone A test piece was obtained in the same manner as in Example 3-29 except that a resin solution was prepared by stirring.

(Example 3-33)
100 parts by mass of Sokkeal SOXR-OB manufactured by Nippon Kogyo Paper Industries Co., Ltd., 1 part by mass of an acrylic copolymer (BYK-361N manufactured by BYK Japan Japan), BYK-313 manufactured by BYK Japan Japan A test piece was obtained in the same manner as in Example 3-29, except that 1.3 parts by mass and 70 parts by mass of methyl ethyl ketone were mixed and stirred to prepare a resin solution.

(Example 3-34)
100 parts by weight of Socsea SOXR-OB manufactured by Nippon Kogyo Paper Industries Co., Ltd., 1 part by weight of an acrylic copolymer (BYK-361N manufactured by Big Chemie Japan Co., Ltd.), and 0.5 parts by weight of MegaFac RS-75 A test piece was obtained in the same manner as in Example 3-29 except that 70 parts by mass of methyl ethyl ketone was blended and stirred to prepare a resin solution.

(Comparative Example 3-12)
Test piece as in Example 3-29 except that 100 parts by weight of Socsea SOXR-OB manufactured by Nippon Kogyo Paper Industries Co., Ltd. and 70 parts by weight of methyl ethyl ketone were mixed and stirred to prepare a resin solution. Got.

(Example 3-35)
In Example 3-14, the sheet-like cellulose nanofiber composite molded body having a thickness of 0.5 mm was overlapped with 18 μm copper foil on the front and back, and a vacuum press machine was used at a temperature of 190 ° C. and a pressure of 0.5 MPa. Heated for minutes. Next, as shown in FIGS. 4A to 4C, a through hole 27 having a drill diameter of 300 μm is formed by drilling on the laminated plate 21 made of the insulating layer 21b having the conductor layer 21a formed on both surfaces thereof. , With a pitch of 5 mm. Thereafter, smear was removed with an aqueous potassium permanganate solution, electroless copper plating treatment, and then electrolytic copper plating treatment were performed to form through holes 28. Next, as shown in FIGS. 5A to 5C, a wiring pattern 26 was produced by an etching method to obtain a test piece.

(Example 3-36)
A test piece was produced in the same manner as in Example 3-35, except that the 0.5 mm thick sheet of Example 3-22 was used.

(Comparative Example 3-13)
A test piece was prepared in the same manner as in Example 3-35 except that the 0.5 mm thick sheet of Comparative Example 3-3 was used.

(Example 3-37)
A test piece was prepared in the same manner as in Example 3-35 except that the 0.5 mm thick sheet of Example 3-15 was used.

(Example 3-38)
A test piece was prepared in the same manner as in Example 3-35 except that the 0.5 mm thick sheet of Example 3-23 was used.

(Comparative Example 3-14)
A test piece was produced in the same manner as in Example 3-35 except that the 0.5 mm thick sheet of Comparative Example 3-4 was used.

(Insulation reliability evaluation)
A direct voltage of 50 V was applied to the electrodes of the six test pieces, and a standing test was performed in an atmosphere of 130 ° C. and 85%. The insulation resistance was measured in the test tank, and the time that became 1/100 of the insulation resistance value one hour after the start of the test was recorded. If the insulation resistance value did not decrease after 100 hours, it was terminated.

As described in detail above, it has been confirmed that the insulation reliability of the insulating material to which cellulose nanofibers are added is dramatically improved by the presence of one or both of a silicone compound and a fluorine compound.

<Example 4>
[Preparation of cellulose fiber dispersion]
Softwood kraft pulp (NBKP) is mechanically treated with a high-pressure homogenizer, and the resulting cellulose fiber with a number average fiber diameter of 3 μm is added to water and stirred sufficiently to produce an aqueous suspension of 10% by weight cellulose fiber. did. This was subjected to dehydration filtration, 10 times the amount of carbitol acetate as the weight of the filtrate was added, and the mixture was stirred for 30 minutes and then filtered. This substitution operation was repeated three times, and 10 times the amount of carbitol acetate by weight of the filtrate was added to prepare a 10% by mass cellulose fiber dispersion.

[Evaluation]
In accordance with the description in Table 24 and Table 25 below, each component was blended, stirred, and dispersed with a three roll to prepare each composition. The obtained composition was printed on the entire surface of a FR-4 copper-clad laminate (copper thickness 18 μm) having a size of 150 mm × 100 mm and a thickness of 1.6 mm by a screen printing method. Curing was carried out at 30 ° C. for 30 minutes. The film thickness after curing was 50 μm. Thereafter, the surface of the cured product was roughened with an aqueous potassium permanganate solution, and electroless copper plating and then electrolytic copper plating were applied to the entire surface to prepare an evaluation substrate. Cut the copper plated part into a 10mm wide and 100mm long part, peel off one end of the copper plated part, grab it with a gripping tool, and peel off 35mm vertically at a speed of 50mm / min at room temperature (Peel strength) was measured.

* 4-1) Thermosetting compound 1: Epicote 828, manufactured by Mitsubishi Chemical Corporation * 4-2) Thermosetting compound 2: Epicote 807, manufactured by Mitsubishi Chemical Corporation * 4-3) Curing catalyst 1: 2MZ-A * 4-4) Colorant: Phthalocyanine Blue * 4-5) Organic solvent: Carbitol acetate

According to the description in Table 26 and Table 27 below, each component was blended, stirred, and dispersed with a three roll to prepare each composition. The obtained composition was printed on the entire surface of a FR-4 copper-clad laminate (copper thickness 18 μm) having a size of 150 mm × 100 mm and a thickness of 1.6 mm by a screen printing method. After drying at 30 ° C. for 30 minutes, it was cured at 170 ° C. for 60 minutes. The film thickness after curing was 50 μm. Thereafter, the surface of the cured product was roughened with an aqueous potassium permanganate solution, and electroless copper plating and then electrolytic copper plating were applied to the entire surface to prepare an evaluation substrate. Cut the copper plated part into a 10mm wide and 100mm long part, peel off one end of the copper plated part, grab it with a gripping tool, and peel off 35mm vertically at a speed of 50mm / min at room temperature (Peel strength) was measured.

* 4-6) Thermosetting compound 3: Unidic V-8000 (solid content 40% by mass) manufactured by DIC Corporation * 4-7) Thermosetting compound 4: Denacol EX-830 manufactured by Nagase ChemteX Corporation * 4-8) Curing catalyst 2: Triphenylphosphine

According to the description in Table 28 and Table 29 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 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.). Cold pressing was performed at 0.5 MPa for 1 minute. As a result, a sheet having a thickness of 50 μm was obtained. This sheet was hot-pressed on a FR-4 copper-clad laminate (copper thickness 18 μm) having a size of 150 mm × 100 mm and a thickness of 1.6 mm by hot pressing at 190 ° C. and 20 MPa for 1 minute, and further at 23 ° C. A test piece was produced by cold pressing at 0.5 MPa for 1 minute. Thereafter, the surface of the cured product was roughened with an aqueous potassium permanganate solution, and electroless copper plating and then electrolytic copper plating were applied to the entire surface to prepare an evaluation substrate. Cut the copper plated part into a 10mm wide and 100mm long part, peel off one end of the copper plated part, grab it with a gripping tool, and peel off 35mm vertically at a speed of 50mm / min at room temperature (Peel strength) was measured.

* 4-9) Thermoplastic resin 1: Novatec PP BC03L manufactured by Nippon Polypro Co., Ltd.

According to the description in Table 30 and Table 31 below, each component was blended 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 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. As a result, a sheet having a thickness of 50 μm was obtained. This sheet was hot-pressed on a FR-4 copper-clad laminate (copper thickness: 18 μm) having a size of 150 mm × 100 mm and a thickness of 1.6 mm by hot pressing at 190 ° C. and 20 MPa for 1 minute. A test piece was produced by cooling and pressing at 5 MPa for 1 minute. Thereafter, the surface of the cured product was roughened with an aqueous potassium permanganate solution, and electroless copper plating and then electrolytic copper plating were applied to the entire surface to prepare an evaluation substrate. Cut the copper plated part into a 10mm wide and 100mm long part, peel off one end of the copper plated part, grab it with a gripping tool, and peel off 35mm vertically at a speed of 50mm / min at room temperature (Peel strength) was measured.

* 4-10) Thermoplastic resin 2: Novatec LDLC561 Made by Nippon Polyethylene Co., Ltd.

According to the description in Table 32 and Table 33 below, each component was blended, stirred, and dispersed with a three roll to prepare each composition. The obtained composition was printed on the entire surface of a FR-4 copper-clad laminate (copper thickness 18 μm) having a size of 150 mm × 100 mm and a thickness of 1.6 mm by a screen printing method, and 120 ° C. in a hot air circulation drying oven. After drying at 10 ° C. for 10 minutes, it was cured at 250 ° C. for 30 minutes. The film thickness after curing was 50 μm. Thereafter, the surface of the cured product was roughened with an aqueous potassium permanganate solution, and electroless copper plating and then electrolytic copper plating were applied to the entire surface to prepare an evaluation substrate. Cut the copper plated part into a 10mm wide and 100mm long part, peel off one end of the copper plated part, grab it with a gripping tool, and peel off 35mm vertically at a speed of 50mm / min at room temperature (Peel strength) was measured.

* 4-11) Thermoplastic resin 3: Socsea SOXR-OB Varnish manufactured by Nippon Kogyo Paper Industry Co., Ltd. (solid content: 70% by mass)

In accordance with the description in Table 34 and Table 35 below, each component was blended, stirred, and dispersed with a three roll to prepare each composition. The obtained composition was printed on the entire surface of a FR-4 copper-clad laminate (copper thickness 18 μm) having a size of 150 mm × 100 mm and a thickness of 1.6 mm by a screen printing method, and a wavelength of 350 nm using a metal halide lamp. Was irradiated with an integrated light amount of ² J / cm ² and cured. The film thickness after curing was 50 μm. Thereafter, the surface of the cured product was roughened with an aqueous potassium permanganate solution, and electroless copper plating and then electrolytic copper plating were applied to the entire surface to prepare an evaluation substrate. Cut the copper plated part into a 10mm wide and 100mm long part, peel off one end of the copper plated part, grab it with a gripping tool, and peel off 35mm vertically at a speed of 50mm / min at room temperature (Peel strength) was measured.

* 4-12) Photocurable compound 1: Bisphenol A type epoxy acrylate Mitsubishi Chemical Corporation * 4-13) Photocurable compound 2: Trimethylolpropane triacrylate * 4-14) Photocurable compound 3: Kayamar PM2 Nippon Kayaku Co., Ltd. * 4-15) Photocurable Compound 4: Light Ester HO Kyoeisha Chemical Co., Ltd. * 4-16) Photopolymerization initiator 1: 2-ethylanthraquinone

In accordance with the description in Table 36 to Table 41 below, each component was blended, stirred, and dispersed with a three roll to prepare each composition. The obtained composition was printed on the entire surface of a FR-4 copper-clad laminate (copper thickness: 18 μm) having a size of 150 mm × 100 mm and a thickness of 1.6 mm by a screen printing method. , And dried at 80 ° C. for 30 minutes. Next, using a negative pattern that can cover 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. Using an aqueous sodium carbonate solution as a developer, development was performed with a printed wiring board developing machine for 60 seconds, and then the edges were thermally cured at 150 ° C. for 60 minutes in a hot-air circulating drying furnace. The film thickness after curing was 50 μm. Thereafter, the surface of the cured product was roughened with an aqueous potassium permanganate solution, and electroless copper plating and then electrolytic copper plating were applied to the entire surface to prepare an evaluation substrate. Cut the copper plated part into a 10mm wide and 100mm long part, peel off one end of the copper plated part, grab it with a gripping tool, and peel off 35mm vertically at a speed of 50mm / min at room temperature (Peel strength) was measured.

* 4-17) Curing catalyst 3: Finely pulverized melamine * 4-18) Curing catalyst 4: Dicyandiamide * 4-19) Photopolymerization initiator 2: Irgacure 907 manufactured by BASF * 4-20) Light Curing compound 5: Dipentaerythritol tetraacrylate * 4-21) Thermosetting compound 5: TEPIC-H Nissan Chemical Co., Ltd.

As detailed above, by using an insulating material containing cellulose nanofibers having a number average fiber diameter of 3 nm or more and less than 1000 nm and cellulose fibers having a number average fiber diameter of 1 μm or more, the peel strength has been dramatically improved. It was.

<Example 5>
[Production of Cellulose Nanofiber Dispersion Having Carboxylate]
(Production Example 1)
2, 2, 6, 6 5 g of softwood bleached kraft pulp (manufactured by Oji Paper Co., Ltd., moisture 50% by mass, Canadian standard freeness (CSF) 550 ml, mainly in an absolutely dry state with a number average fiber diameter exceeding 1000 nm) -Tetramethylpiperidine-N-oxyl (TEMPO) 79 mg (0.5 mmol) and sodium bromide 515 mg (5 mmol) were added to 500 ml of an aqueous solution and stirred until the pulp was uniformly dispersed. To this, 18 ml of an aqueous sodium hypochlorite solution containing 5% effective chlorine was added, the pH was adjusted to 10 with an aqueous 0.5N hydrochloric acid solution, and an oxidation reaction was started. During the reaction, the pH in the system was lowered, but a 0.5N aqueous sodium hydroxide solution was successively added to adjust the pH to 10. After the reaction for 2 hours, the mixture was filtered through a glass filter, and the residue was sufficiently washed with water to obtain a reaction product.

Next, distilled water was added to the reaction product to obtain an aqueous dispersion having a pulp concentration of 2% by mass, and the mixture was stirred and dispersed with a rotary blade mixer for 5 minutes. Since the viscosity of the slurry significantly increased with stirring, distilled water was added little by little, and stirring and dispersion with a mixer was continued until the solid content concentration reached 0.2% by mass to obtain a transparent gelled aqueous solution. This was observed with TEM and confirmed to be an aqueous dispersion of cellulose nanofibers having a carboxylate having a number average fiber diameter of 10 nm. The amount of carboxyl groups in the aqueous dispersion was 1.25 mmol / g.

This was dehydrated and filtered, 10 times the weight of the filtrate was added, carbitol acetate was added, and the mixture was stirred for 30 minutes and then filtered. This substitution operation was repeated three times to add 10 times the amount of carbitol acetate as the weight of the filtrate to prepare cellulose nanofiber dispersion 1 having 10% by mass of carboxylate.

(Production Example 2)
Instead of 79 mg (0.5 mmol) of 2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO), 4-dimethylamino-2,2,6,6-tetramethylpiperidine-N-oxyl (4- A cellulose nanofiber dispersion 2 having 10% by mass of a carboxylate was prepared in the same manner as in Production Example 1 except that 100 mg (0.5 mmol) of (dimethylamino-TEMPO) was used. The amount of carboxyl groups in the aqueous dispersion was 1.30 mmol / g, and the number average fiber diameter of the cellulose nanofibers having a carboxylate salt was 12 nm.

(Production Example 3)
Instead of 79 mg (0.5 mmol) of 2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO), 4-carboxy-2,2,6,6-tetramethylpiperidine-N-oxyl (4-carboxyl) A cellulose nanofiber dispersion 3 having 10% by mass of carboxylate was prepared in the same manner as in Production Example 1 except that 101 mg (0.5 mmol) of -TEMPO) was used. The amount of carboxyl groups in the aqueous dispersion was 1.16 mmol / g, and the number average fiber diameter of the cellulose nanofibers having a carboxylate salt was 10 nm.

[Production of cellulose nanofiber dispersion]
(Production Example 4)
A plate made of eucalyptus was pulverized using a cutter mill to produce a wood powder of about 0.2 mm square. Next, this wood flour was subjected to high-temperature and high-pressure treatment in an aqueous solution such as sodium sulfite and sodium hydroxide to remove lignin. 50 times distilled water was added and stirred, and after mechanical pulverization using a disk mill 15 times, distilled water was added and stirred to 10% by mass, and cellulose nanofibers having a number average fiber diameter of 80 nm Got. This was subjected to dehydration filtration, 10 times the amount of carbitol acetate as the weight of the filtrate was added, and the mixture was stirred for 30 minutes and then 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 1.

* 5-1) Thermosetting compound 1: Epicoat 828, manufactured by Mitsubishi Chemical Corporation * 5-2) Thermosetting compound 2: Epicoat 807, manufactured by Mitsubishi Chemical Corporation * 5-3) Curing catalyst 1: 2MZ-A Shikoku Kasei Kogyo Co., Ltd. * 5-4) Colorant: Phthalocyanine Blue * 5-5) Organic solvent: Carbitol acetate

* 5-6) Thermoset 1 compound 3: Unidic V-8000 manufactured by DIC Corporation (solid content 40% by mass)
* 5-7) Thermosetting compound 4: Denacol EX-830, manufactured by Nagase ChemteX Corporation * 5-8) Curing catalyst 2: Triphenylphosphine

* 5-9) Thermoplastic resin 1: Socsea SOXR-OB Varnish manufactured by Nippon Kogyo Paper Industries Co., Ltd. (solid content 70% by mass, N-methylpyrrolidone 30% by mass)

* 5-10) Photocurable compound 1: Bisphenol A type epoxy acrylate Mitsubishi Chemical Corporation * 5-11) Photocurable compound 2: Trimethylolpropane triacrylate * 5-12) Photocurable compound 3: Kayamar PM2 Nippon Kayaku Co., Ltd. * 5-13) Photocurable Compound 4: Light Ester HO Kyoeisha Chemical Co., Ltd. * 5-14) Photopolymerization initiator 1: 2-ethylanthraquinone

* 5-15) Curing catalyst 3: Finely pulverized melamine * 5-16) Curing catalyst 4: Dicyandiamide * 5-17) Photopolymerization initiator 2: Irgacure 907 manufactured by BASF * 5-18) Photocuring Compound 5: dipentaerythritol tetraacrylate * 5-19) thermosetting compound 5: TEPIC-H manufactured by Nissan Chemical Co., Ltd.

[Production of sheet for evaluation of breaking strength and breaking elongation]
In accordance with the description in Table 42 above, each component was blended, stirred, and dispersed with a three roll to prepare each composition. 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 an evaluation sheet having a thickness of 50 μm.

According to the description in Table 43 above, each component was blended, stirred, and dispersed with a three roll to prepare each composition. 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 to prepare an evaluation sheet having a thickness of 50 μm.

According to the description in Table 44 above, each component was blended, stirred, and dispersed with a three roll to prepare each composition. 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 to prepare an evaluation sheet having a thickness of 50 μm.

In accordance with the description in Table 45 above, each component was blended, stirred, and dispersed with a three roll to prepare each composition. 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 to prepare an evaluation sheet having a thickness of 50 μm.

According to the descriptions in Tables 46 to 48, each component was blended, stirred, and dispersed with a three roll to prepare each composition. 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 center of the copper foil, the printed wiring board exposure machine HMW-680GW (manufactured by Oak Manufacturing Co., Ltd.) was 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 copper foil edge was removed. Subsequently, it was cured at 150 ° C. for 60 minutes in a hot air circulating drying oven. Thereafter, the copper foil was removed to prepare an evaluation sheet having a thickness of 50 μm.

[Evaluation of breaking strength and breaking elongation]
Based on JIS K7127, the said evaluation sheet | seat was cut | judged to the predetermined magnitude | size, and the test piece was produced. After measuring the breaking strength [MPa] and breaking elongation [%] of this test piece using a tensile testing machine (AGS-G manufactured by Shimadzu Corporation) at a pulling speed of 10 mm / min, the following evaluation criteria were satisfied. Based on the evaluation. The results are shown in Table 49 to Table 52 below. In the evaluation criteria of the breaking strength and breaking elongation, when both are good, it can be seen that the cured product of the test piece has high toughness and excellent crack resistance.

(Evaluation criteria for breaking strength)
○: 75 MPa or more Δ: 50 MPa or more and less than 75 MPa x: less than 50 MPa (Evaluation criteria for breaking elongation)
○: 6% or more Δ: 4% or more and less than 6% ×: less than 4%

[Preparation of crack resistance evaluation substrate]
In the preparation of the above-mentioned breaking strength and breaking elongation evaluation sheet, an FR-4 copper-clad laminate (copper thickness 18 μm) having a thickness of 1.6 mm was used instead of the copper foil, and a cured product having a thickness of 20 μm was obtained. Went through the same steps to produce an evaluation substrate having a cured product formed on a copper-clad laminate.

[Evaluation of crack resistance]
The evaluation substrate was given a temperature history of 1000 cycles with one cycle of −65 ° C. for 30 minutes and 150 ° C. for 30 minutes, and the degree of cracking and peeling of the evaluation substrate thereafter was measured with an optical microscope (Corporation). Observation was carried out with VHX-2000 (manufactured by Keyence), and evaluation was performed based on the following evaluation criteria. The results are shown in Table 49 to Table 52 below.
(Evaluation criteria)
○: No crack is generated Δ: Crack is generated ×: Crack is significantly generated

As described in detail above, it was confirmed that the crack resistance can be improved by using a printed wiring board material containing cellulose nanofibers having a carboxylate.

<Example 6>
[Production of lignocellulose nanofiber dispersion]
(Production Example 1)
A plate made of eucalyptus was pulverized using a cutter mill to produce a wood powder of about 0.2 mm square. Next, 50 times the mass of distilled water is added to this wood flour and stirred. After 15 times of mechanical pulverization using a disk mill, distilled water is added to a mass of 10% and stirred. Thus, cellulose nanofibers having a number average fiber diameter of 80 nm were obtained. This was subjected to dehydration filtration, 10 times the amount of carbitol acetate as the weight of the filtrate was added, and the mixture was stirred for 30 minutes and then filtered. This substitution operation was repeated three times, and 10 times the amount of carbitol acetate as the weight of the filtrate was added to prepare a 10 mass% lignocellulose nanofiber dispersion 1.

(Production Example 2)
A board made of cedar was pulverized using a cutter mill to produce a wood powder of about 0.2 mm square. Next, 50 times the mass of distilled water is added to this wood flour and stirred. After 15 times of mechanical pulverization using a disk mill, distilled water is added to a mass of 10% and stirred. Thus, cellulose nanofibers having a number average fiber diameter of 80 nm were obtained. This was subjected to dehydration filtration, 10 times the amount of carbitol acetate as the weight of the filtrate was added, and the mixture was stirred for 30 minutes and then filtered. This substitution operation was repeated three times, 10 times the amount of carbitol acetate as the weight of the filtrate was added, and 10 mass% lignocellulose nanofiber dispersion liquid 2 was produced.

[Production of comparative cellulose nanofiber dispersion]
(Production Example 3)
A plate made of eucalyptus was pulverized using a cutter mill to produce a wood powder of about 0.2 mm square. Next, this wood flour was subjected to high-temperature and high-pressure treatment in an aqueous solution such as sodium sulfite and sodium hydroxide to remove lignin. 50 times distilled water was added thereto and stirred, and after mechanical grinding using a disk mill 15 times, distilled water was added and stirred so as to be 10% by mass, and cellulose having a number average fiber diameter of 80 nm. Nanofibers were obtained. This was subjected to dehydration filtration, 10 times the amount of carbitol acetate as the weight of the filtrate was added, and the mixture was stirred for 30 minutes and then 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 1.

[Preparation of printed wiring board materials]
According to the descriptions in Table 53, Table 54, and Tables 57 to 61 below, the respective components were blended, stirred, and dispersed by a three roll to prepare each composition. In addition, all the numbers in the following table | surface show a mass part.

Each component was blended according to the description in Table 55 below, 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 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.). Cold pressing was performed at 0.5 MPa for 1 minute. Thereby, sheet-like cellulose nanofiber composite molded bodies having a thickness of 0.5 mm and 0.05 mm were obtained, respectively.

According to the description in Table 56 below, each component was blended 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 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. Thereby, sheet-like cellulose nanofiber composite molded bodies having a thickness of 0.5 mm and 0.05 mm were obtained, respectively.

* 6-1) Thermosetting compound 1: Epicoat 828, manufactured by Mitsubishi Chemical Corporation * 6-2) Thermosetting compound 2: Epicoat 807, manufactured by Mitsubishi Chemical Corporation * 6-3) Curing catalyst 1: 2MZ-A * 6-4) Pigment: phthalocyanine blue * 6-5) Organic solvent: Carbitol acetate

* 6-6) Thermosetting compound 3: Unidic V-8000 manufactured by DIC Corporation (solid content 40% by mass)
* 6-7) Thermosetting compound 4: Denacol EX-830, manufactured by Nagase ChemteX Corporation * 6-8) Curing catalyst 2: Triphenylphosphine

* 6-9) Thermoplastic resin 1: Novatec PP BC03L manufactured by Nippon Polypro Co., Ltd.

* 6-10) Thermoplastic resin 2: Novatec LD LC561, manufactured by Nippon Polyethylene Co., Ltd.

* 6-11) Thermoplastic resin 3: Socsea SOXR-OB Varnish manufactured by Nippon Kogyo Paper Industries Co., Ltd. (solid content 70% by mass, N-methylpyrrolidone 30% by mass)

* 6-12) Photocurable compound 1: bisphenol A type epoxy acrylate Mitsubishi Chemical Corporation * 6-13) Photocurable compound 2: Trimethylolpropane triacrylate * 6-14) Photocurable compound 3: Kayamar PM2 Nippon Kayaku Co., Ltd. * 6-15) Photocurable compound 4: Light ester HO Kyoeisha Chemical Co., Ltd. * 6-16) Photopolymerization initiator 1: 2-ethylanthraquinone

* 6-17) Curing catalyst 3: Finely pulverized melamine (manufactured by Nissan Chemical Co., Ltd.)
* 6-18) Curing catalyst 4: Dicyandiamide * 6-19) Photopolymerization initiator 2: Irgacure 907 (BASF)
* 6-20) Photocurable compound 5: Dipentaerythritol tetraacrylate * 6-21) Thermosetting compound 5: TEPIC-H (manufactured by Nissan Chemical Co., Ltd.)

[Evaluation as solder resist]
(Production of test substrate)
Using an FR-4 copper-clad laminate (copper thickness 9 μm) having a size of 100 mm × 150 mm and a thickness of 1.6 mm, an IPC standard B pattern comb-shaped electrode pattern was produced by an etching method.

On the test substrate, the compositions of Examples 6-1 to 6-6 and Comparative Examples 6-1 and 6-2 were printed by screen printing so as to cover the comb electrodes, A test piece was prepared by curing in a circulation drying oven at 140 ° C. for 30 minutes.
As a withstand voltage test, a DC voltage was applied to each of the six test pieces at a boosting speed of 500 V / second to measure the breakdown voltage. The case where the average of 6 sheets was 4.5 kV or more was evaluated as ◯, and the case where it was less than 4.5 kV was evaluated as ×. As a result, the results for Examples 6-1 to 6-6 were all “good”, and the results for comparative examples 6-1 and 6-2 were all “x”.
In addition, as an insulation reliability test, a DC voltage of 50 V was applied to each of six test pieces, a standing test was performed in an atmosphere of 130 ° C. and 85% RH, and the time until short-circuiting was measured. The case where the average of 6 sheets was 200 hours or more was evaluated as “◯”, and the case where it was less than 200 hours was evaluated as “X”. As a result, the results for Examples 6-1 to 6-6 were all “good”, and the results for comparative examples 6-1 and 6-2 were all “x”.

On the test substrate, the compositions of Examples 6-7 to 6-12 and Comparative Examples 6-3 and 6-4 were printed by screen printing so as to cover the comb electrodes, After drying at 100 ° C. for 30 minutes in a circulation drying oven, the test piece was cured by curing at 170 ° C. for 60 minutes.
As a withstand voltage test, a DC voltage was applied to each of the six test pieces at a boosting speed of 500 V / second to measure the breakdown voltage. The case where the average of 6 sheets was 5.5 kV or more was evaluated as ◯, and the case where it was less than 5.5 kV was evaluated as x. As a result, all of Examples 6-7 to 6-12 were evaluated as ◯, and those of Comparative Examples 6-3 and 6-4 were evaluated as x.
In addition, as an insulation reliability test, a DC voltage of 50 V was applied to each of six test pieces, a standing test was performed in an atmosphere of 130 ° C. and 85% RH, and the time until short-circuiting was measured. The case where the average of 6 sheets was 300 hours or more was evaluated as ◯, and the case where it was less than 300 hours was evaluated as ×. As a result, all of Examples 6-7 to 6-12 were “good”, and those of Comparative Examples 6-3 and 6-4 were all “x”.

On the test substrate, the 0.05 mm-thick sheets of Examples 6-13 to 6-24 and Comparative Examples 6-5 to 6-8 were cut and processed so as to cover the comb-shaped electrodes. Then, hot pressing was performed at 190 ° C. and 20 MPa for 1 minute by hot pressing, and further cooling pressing was performed at 23 ° C. and 0.5 MPa for 1 minute to prepare a test piece.
As a withstand voltage test, a DC voltage was applied to each of the six test pieces at a boosting speed of 500 V / second to measure the breakdown voltage. The case where the average of 6 sheets was 3.5 kV or more was evaluated as ◯, and the case where it was less than 3.5 kV was evaluated as ×. As a result, all of Examples 6-13 to 6-24 were ○, and all of Comparative Examples 6-5 to 6-8 were ×.
In addition, as an insulation reliability test, a DC voltage of 50 V was applied to each of six test pieces, a standing test was performed in an atmosphere of 130 ° C. and 85% RH, and the time until short-circuiting was measured. The case where the average of 6 sheets was 250 hours or more was evaluated as ◯, and the case where it was less than 250 hours was evaluated as ×. As a result, all of Examples 6-13 to 6-24 were ○, and all of Comparative Examples 6-5 to 6-8 were ×.

On the test substrate, the compositions of Examples 6-25 to 6-30 and Comparative Examples 6-9 and 6-10 were printed by a screen printing method so as to cover the comb electrodes, After drying at 120 ° C. for 10 minutes in a circulation drying furnace, the test piece was cured by curing at 250 ° C. for 30 minutes.
As a withstand voltage test, a DC voltage was applied to each of the six test pieces at a boosting speed of 500 V / second to measure the breakdown voltage. The case where the average of 6 sheets was 5.5 kV or more was evaluated as ◯, and the case where it was less than 5.5 kV was evaluated as x. The results of Examples 6-25 to 6-30 were all “good”, and those of Comparative Examples 6-9 and 6-10 were all “x”.
In addition, as an insulation reliability test, a DC voltage of 50 V was applied to each of six test pieces, a standing test was performed in an atmosphere of 130 ° C. and 85% RH, and the time until short-circuiting was measured. The case where the average of 6 sheets was 250 hours or more was evaluated as ◯, and the case where it was less than 250 hours was evaluated as ×. The results of Examples 6-25 to 6-30 were all “good”, and those of Comparative Examples 6-9 and 6-10 were all “x”.

On the test substrate, the compositions of Examples 6-31 to 6-36 and Comparative Examples 6-11 and 6-12 were printed by the screen printing method so as to cover the comb electrodes. Then, an accumulated light amount of ² J / cm ² was irradiated with a metal halide lamp at a wavelength of 350 nm and cured to prepare a test piece.
As a withstand voltage test, a DC voltage was applied to each of the six test pieces at a boosting speed of 500 V / second to measure the breakdown voltage. The case where the average of 6 sheets was 3.5 kV or more was evaluated as ◯, and the case where it was less than 3.5 kV was evaluated as ×. As a result, all of Examples 6-31 to 6-36 were “good”, and those of Comparative Examples 6-11 and 6-12 were all “x”.
In addition, as an insulation reliability test, a DC voltage of 50 V was applied to each of six test pieces, a standing test was performed in an atmosphere of 130 ° C. and 85% RH, and the time until short-circuiting was measured. The case where the average of 6 sheets was 100 hours or more was evaluated as ◯, and the case where it was less than 100 hours was evaluated as ×. As a result, all of Examples 6-31 to 6-36 were “good”, and those of Comparative Examples 6-11 and 6-12 were all “x”.

On the test substrate, the compositions of Examples 6-37 to 6-54 and Comparative Examples 6-13 to 6-18 were applied to the entire surface by screen printing using a 100 mesh polyester bias plate. Printed and dried in a hot air circulating drying oven at 80 ° C. for 30 minutes. Next, using a negative pattern that can be covered with a comb-shaped electrode, exposure is performed with an integrated light quantity of 700 mJ / cm ^{2 with} an exposure machine HMW-680GW (manufactured by Oak Manufacturing Co., Ltd.) for printed wiring boards, and 1% at 30 ° C. Using a sodium carbonate aqueous solution as a developer, development was performed for 60 seconds with a developing machine for printed wiring boards, followed by heat curing at 150 ° C. for 60 minutes in a hot-air circulating drying furnace to prepare test pieces.
As a withstand voltage test, a DC voltage was applied to each of the six test pieces at a boosting speed of 500 V / second to measure the breakdown voltage. The case where the average of 6 sheets was 4.5 kV or more was evaluated as ◯, and the case where it was less than 4.5 kV was evaluated as ×. As a result, all of Examples 6-37 to 6-54 were “good”, and those of Comparative Examples 6-13 to 6-18 were all “x”.
In addition, as an insulation reliability test, a DC voltage of 50 V was applied to each of six test pieces, a standing test was performed in an atmosphere of 130 ° C. and 85% RH, and the time until short-circuiting was measured. The case where the average of 6 sheets was 200 hours or more was evaluated as “◯”, and the case where it was less than 200 hours was evaluated as “X”. As a result, all of Examples 6-37 to 6-54 were “good”, and those of Comparative Examples 6-13 to 6-18 were all “x”.

[Evaluation as interlayer insulation material]
The compositions of Example 6-1 to Example 6-6 and Comparative Examples 6-1 and 6-2 were combined with an FR-4 copper-clad laminate (copper thickness) having a size of 100 mm × 150 mm and a thickness of 1.6 mm. 9 μm) was printed on the entire surface by a screen printing method, and cured in a hot air circulating drying oven at 140 ° C. for 30 minutes. Next, electroless copper plating was applied, and then electrolytic copper plating was applied. Thereafter, a test piece having an IPC standard B pattern comb-shaped electrode pattern was produced by an etching method.
As a withstand voltage test, a DC voltage was applied to each of the six test pieces at a boosting speed of 500 V / second to measure the breakdown voltage. The case where the average of 6 sheets was 5.5 kV or more was evaluated as ◯, and the case where it was less than 5.5 kV was evaluated as x. As a result, the results for Examples 6-1 to 6-6 were all “good”, and the results for comparative examples 6-1 and 6-2 were all “x”.
In addition, as an insulation reliability test, a DC voltage of 50 V was applied to each of six test pieces, a standing test was performed in an atmosphere of 130 ° C. and 85% RH, and the time until short-circuiting was measured. The case where the average of 6 sheets was 400 hours or more was evaluated as “◯”, and the case where it was less than 400 hours was evaluated as “X”. As a result, the results for Examples 6-1 to 6-6 were all “good”, and the results for comparative examples 6-1 and 6-2 were all “x”.

The compositions of Examples 6-7 to 6-12 and Comparative Examples 6-3 and 6-4 were combined with an FR-4 copper-clad laminate (copper thickness of 100 mm × 150 mm and 1.6 mm thickness). 9 μm) was printed 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 cured at 170 ° C. for 60 minutes. Next, electroless copper plating was applied, and then electrolytic copper plating was applied. Thereafter, a test piece having an IPC standard B pattern comb-shaped electrode pattern was produced by an etching method.
As a withstand voltage test, a DC voltage was applied to each of the six test pieces at a boosting speed of 500 V / second to measure the breakdown voltage. The case where the average of 6 sheets was 6.5 kV or more was evaluated as ◯, and the case where it was less than 6.5 kV was evaluated as ×. As a result, all of Examples 6-7 to 6-12 were “good”, and those of Comparative Examples 6-3 and 6-4 were all “x”.
In addition, as an insulation reliability test, a DC voltage of 50 V was applied to each of six test pieces, a standing test was performed in an atmosphere of 130 ° C. and 85% RH, and the time until short-circuiting was measured. The average of 6 sheets was evaluated as “◯” when the average was 500 hours or more, and “×” when the average was less than 500 hours. The results of Examples 6-7 to 6-12 were all “good”, and those of Comparative Examples 6-3 and 6-4 were all “x”.

Sheets having a thickness of 0.05 mm in Examples 6-13 to 6-24 and Comparative Examples 6-5 to 6-8 were FR-4 having a size of 100 mm × 150 mm and a thickness of 1.6 mm. A copper-clad laminate (copper thickness 9 μm) was hot-pressed by hot pressing at 190 ° C. and 20 MPa for 1 minute, and further cold-pressed by 23 ° C. and 0.5 MPa for 1 minute. Next, electroless copper plating was applied, and then electrolytic copper plating was applied. Thereafter, a test piece having an IPC standard B pattern comb-shaped electrode pattern was produced by an etching method.
As a withstand voltage test, a DC voltage was applied to each of the six test pieces at a boosting speed of 500 V / second to measure the breakdown voltage. The case where the average of 6 sheets was 4.5 kV or more was evaluated as ◯, and the case where it was less than 4.5 kV was evaluated as ×. As a result, all of Examples 6-13 to 6-24 were ○, and all of Comparative Examples 6-5 to 6-8 were ×.
In addition, as an insulation reliability test, a DC voltage of 50 V was applied to each of six test pieces, a standing test was performed in an atmosphere of 130 ° C. and 85% RH, and the time until short-circuiting was measured. The case where the average of 6 sheets was 400 hours or more was evaluated as “◯”, and the case where it was less than 400 hours was evaluated as “X”. As a result, all of Examples 6-13 to 6-24 were ○, and all of Comparative Examples 6-5 to 6-8 were ×.

The compositions of Examples 6-25 to 6-30 and Comparative Examples 6-9 and 6-10 were FR-4 copper-clad laminates (copper thickness) having a size of 100 mm × 150 mm and a thickness of 1.6 mm. 9 μm) was printed on the entire surface by a screen printing method, dried in a hot air circulation drying oven at 120 ° C. for 10 minutes, and then cured at 250 ° C. for 30 minutes. Next, electroless copper plating was applied, and then electrolytic copper plating was applied. Thereafter, a test piece having an IPC standard B pattern comb-shaped electrode pattern was produced by an etching method.
As a withstand voltage test, a DC voltage was applied to each of the six test pieces at a boosting speed of 500 V / second to measure the breakdown voltage. The case where the average of 6 sheets was 6 kV or more was evaluated as ◯, and the case where it was less than 6 kV was evaluated as ×. The results of Examples 6-25 to 6-30 were all “good”, and those of Comparative Examples 6-9 and 6-10 were all “x”.
In addition, as an insulation reliability test, a DC voltage of 50 V was applied to each of six test pieces, a standing test was performed in an atmosphere of 130 ° C. and 85% RH, and the time until short-circuiting was measured. The case where the average of 6 sheets was 400 hours or more was evaluated as “◯”, and the case where it was less than 400 hours was evaluated as “X”. The results of Examples 6-25 to 6-30 were all “good”, and those of Comparative Examples 6-9 and 6-10 were all “x”.

The compositions of Examples 6-31 to 6-36 and Comparative Examples 6-11 and 6-12 were FR-4 copper clad laminates (copper thickness) having a size of 100 mm × 150 mm and a thickness of 1.6 mm. 9 μm) was printed on the entire surface by a screen printing method, and then cured by irradiating an integrated light amount of ² J / cm ² at a wavelength of 350 nm with a metal halide lamp. Next, electroless copper plating was applied, and then electrolytic copper plating was applied. Thereafter, a test piece having an IPC standard B pattern comb-shaped electrode pattern was produced by an etching method.
As a withstand voltage test, a DC voltage was applied to each of the six test pieces at a boosting speed of 500 V / second to measure the breakdown voltage. The case where the average of 6 sheets was 4.5 kV or more was evaluated as ◯, and the case where it was less than 4.5 kV was evaluated as ×. As a result, all of Examples 6-31 to 6-36 were “good”, and those of Comparative Examples 6-11 and 6-12 were all “x”.
In addition, as an insulation reliability test, a DC voltage of 50 V was applied to each of six test pieces, a standing test was performed in an atmosphere of 130 ° C. and 85% RH, and the time until short-circuiting was measured. The case where the average of 6 sheets was 250 hours or more was evaluated as ◯, and the case where it was less than 250 hours was evaluated as ×. As a result, all of Examples 6-31 to 6-36 were “good”, and those of Comparative Examples 6-11 and 6-12 were all “x”.

The compositions of Examples 6-37 to 6-54 and Comparative Examples 6-13 to 6-18 were combined with an FR-4 copper-clad laminate (100 mm × 150 mm and 1.6 mm thick). A copper mesh thickness of 9 μm) was printed on the entire surface by screen printing using a 100 mesh polyester bias plate and dried in a hot air circulation drying oven at 80 ° C. for 30 minutes. Next, using a transparent PET film instead of the negative pattern, the printed wiring board exposure machine HMW-680GW (Oak Manufacturing Co., Ltd.) was exposed with an integrated light amount of 700 mJ / cm ² and 1% at 30 ° C. Using an aqueous sodium carbonate solution as a developing solution, development was performed with a developing machine for printed wiring boards for 60 seconds, followed by heat curing at 150 ° C. for 60 minutes in a hot air circulation drying oven. Next, electroless copper plating was applied, and then electrolytic copper plating was applied. Thereafter, a test piece having an IPC standard B pattern comb-shaped electrode pattern was produced by an etching method.
As a withstand voltage test, a DC voltage was applied to each of the six test pieces at a boosting speed of 500 V / second to measure the breakdown voltage. The case where the average of 6 sheets was 5.5 kV or more was evaluated as ◯, and the case where it was less than 5.5 kV was evaluated as x. As a result, all of Examples 6-37 to 6-54 were “good”, and those of Comparative Examples 6-13 to 6-18 were all “x”.
In addition, as an insulation reliability test, a DC voltage of 50 V was applied to each of six test pieces, a standing test was performed in an atmosphere of 130 ° C. and 85% RH, and the time until short-circuiting was measured. The case where the average of 6 sheets was 400 hours or more was evaluated as “◯”, and the case where it was less than 400 hours was evaluated as “X”. As a result, all of Examples 6-37 to 6-54 were “good”, and those of Comparative Examples 6-13 to 6-18 were all “x”.

[Evaluation as core material]
(Preparation of lignocellulose nanofiber sheet)
About lignocellulose nanofiber dispersion liquid 1 and lignocellulose nanofiber dispersion liquid 2, a 0.2% by mass dispersion liquid is prepared with carbitol acetate, filtered through a glass filter, and has a size of 100 mm × 150 mm and a thickness of 40 μm. A sheet was produced.

(Production of cellulose nanofiber sheet)
About the cellulose nanofiber dispersion liquid 1, 0.2 mass% dispersion liquid was produced with carbitol acetate, and it filtered with the glass filter, and produced the sheet | seat of the size of 100 mm x 150 mm, and thickness 40 micrometers.

50 parts by mass of Epicoat 828 manufactured by Mitsubishi Chemical Corporation, 50 parts by mass of Epicoat 807 manufactured by Mitsubishi Chemical Corporation, 3 parts by mass of 2MZ-A manufactured by Shikoku Kasei Kogyo Co., Ltd., and 100 parts by mass of methyl ethyl ketone And stirred to obtain a resin solution. This was impregnated into each cellulose nanofiber sheet, left in an atmosphere at 50 ° C. for 12 hours, then taken out and dried at 80 ° C. for 5 hours to prepare a prepreg. Ten prepregs were stacked, and a copper foil having a thickness of 18 μm was stacked on the front and back, and cured for 3 hours in a vacuum press at a temperature of 160 ° C. and a pressure of 2 MPa. Thereafter, a test piece having an IPC standard B pattern comb-shaped electrode pattern was produced by an etching method. The test piece of lignocellulose nanofiber dispersion 1 was Example 6-55, the test piece of lignocellulose nanofiber dispersion 2 was Example 6-56, the test piece of cellulose nanofiber dispersion 1 was Comparative Example 6-19, Further, a glass cloth was used instead of the cellulose nanofiber, and a similar product was made as Comparative Example 6-20. In Example 6-55, Example 6-56, Comparative Example 6-19, and Comparative Example 6-20, the filling rate of the cellulose fiber was 30% by mass. In Examples 6-55 and 6-56, 1 part by mass of an acrylic copolymer compound (BYK-361N manufactured by Big Chemie Japan Co., Ltd.) was added.
As a withstand voltage test, a DC voltage was applied to each of the six test pieces at a boosting speed of 500 V / second to measure the breakdown voltage. The case where the average of 6 sheets was 5.5 kV or more was evaluated as ◯, and the case where it was less than 5.5 kV was evaluated as x. As a result, the samples of Examples 6-55 and 6-56 were all “good”, and the samples of Comparative Examples 6-19 and 6-20 were all “×”.
In addition, as an insulation reliability test, a DC voltage of 50 V was applied to each of six test pieces, a standing test was performed in an atmosphere of 130 ° C. and 85% RH, and the time until short-circuiting was measured. The case where the average of 6 sheets was 400 hours or more was evaluated as “◯”, and the case where it was less than 400 hours was evaluated as “X”. As a result, the samples of Examples 6-55 and 6-56 were all “good”, and the samples of Comparative Examples 6-19 and 6-20 were all “×”.

100 parts by weight of Unidic V-8000 manufactured by DIC Corporation, 23 parts by weight of Denacor EX-830 manufactured by Nagase ChemteX Corporation, 1 part by weight of triphenylphosphine, and 100 parts by weight of methyl ethyl ketone are mixed and stirred. Thus, a resin solution was obtained. This was impregnated into each cellulose nanofiber sheet, left in an atmosphere at 50 ° C. for 12 hours, then taken out and dried at 80 ° C. for 5 hours to prepare a prepreg. Ten prepregs were stacked, and 18 μm copper foils were stacked on the front and back, and cured for 3 hours at 160 ° C. under a pressure of 2 MPa with a vacuum press. Thereafter, a test piece having an IPC standard B pattern comb-shaped electrode pattern was produced by an etching method. The test piece of lignocellulose nanofiber dispersion 1 was Example 6-57, the test piece of lignocellulose nanofiber dispersion 2 was Example 6-58, the test piece of cellulose nanofiber dispersion 1 was Comparative Example 6-21, Further, a glass cloth was used instead of cellulose nanofiber, and a similar product was produced as Comparative Example 6-22. In Example 6-57, Example 6-58, Comparative Example 6-21, and Comparative Example 6-22, the filling rate of the cellulose fibers was 30% by mass. In Examples 6-57 and 6-58, 1 part by mass of an acrylic copolymer compound (BYK-361N manufactured by Big Chemie Japan Co., Ltd.) was added.
As a withstand voltage test, a DC voltage was applied to each of the six test pieces at a boosting speed of 500 V / second to measure the breakdown voltage. The case where the average of 6 sheets was 6.5 kV or more was evaluated as ◯, and the case where it was less than 6.5 kV was evaluated as ×. As a result, the samples of Examples 6-57 and 6-58 were all “good”, and the samples of Comparative Examples 6-21 and 6-22 were all “×”.
In addition, as an insulation reliability test, a DC voltage of 50 V was applied to each of six test pieces, a standing test was performed in an atmosphere of 130 ° C. and 85% RH, and the time until short-circuiting was measured. The case where the average of 6 sheets was 500 hours or more was evaluated as “◯”, and the case where it was less than 500 hours was evaluated as “X”. As a result, the samples of Examples 6-57 and 6-58 were all “good”, and the samples of Comparative Examples 6-21 and 6-22 were all “×”.

100 parts by mass of Socsea SOXR-OB manufactured by Nippon Kogyo Paper Industries Co., Ltd. and 70 parts by mass of methyl ethyl ketone were mixed and stirred to obtain a resin solution. This was impregnated into each cellulose nanofiber sheet, left in an atmosphere at 50 ° C. for 12 hours, then taken out and dried at 80 ° C. for 5 hours to prepare a prepreg. Ten prepregs were stacked, and 18 μm copper foils were stacked on the front and back, and cured for 3 hours at 160 ° C. under a pressure of 2 MPa with a vacuum press. Thereafter, a test piece having an IPC standard B pattern comb-shaped electrode pattern was produced by an etching method. The test piece of lignocellulose nanofiber dispersion 1 was Example 6-59, the test piece of lignocellulose nanofiber dispersion 2 was Example 6-60, the test piece of cellulose nanofiber dispersion 1 was Comparative Example 6-23, Further, a glass cloth was used in place of the cellulose nanofiber, and a similar product was made as Comparative Example 6-24. In Example 6-59, Example 6-60, Comparative Example 6-23, and Comparative Example 6-24, the cellulose fiber filling factor was 30% by mass. In Examples 6-59 and 6-60, 1 part by mass of an acrylic copolymer compound (BYK-361N manufactured by Big Chemie Japan Co., Ltd.) was added.
As a withstand voltage test, a DC voltage was applied to each of the six test pieces at a boosting speed of 500 V / second to measure the breakdown voltage. The case where the average of 6 sheets was 6 kV or more was evaluated as ◯, and the case where it was less than 6 kV was evaluated as ×. The results of Examples 6-59 and 6-60 were all “good”, and those of Comparative Examples 6-23 and 6-24 were all “x”.
In addition, as an insulation reliability test, a DC voltage of 50 V was applied to each of six test pieces, a standing test was performed in an atmosphere of 130 ° C. and 85% RH, and the time until short-circuiting was measured. The case where the average of 6 sheets was 400 hours or more was evaluated as “◯”, and the case where it was less than 400 hours was evaluated as “X”. The results of Examples 6-59 and 6-60 were all “good”, and those of Comparative Examples 6-23 and 6-24 were all “x”.

18 μm copper foils were stacked on both sides of the 0.5 mm thick sheets of Examples 6-13 to 6-24 and Comparative Examples 6-5 to 6-8, and the temperature was 190 ° C. with a vacuum press. Heating was performed for 1 minute under the condition of a pressure of 0.5 MPa. Thereafter, a test piece having an IPC standard B pattern comb-shaped electrode pattern was produced by an etching method.
As a withstand voltage test, a DC voltage was applied to each of the six test pieces at a boosting speed of 500 V / second to measure the breakdown voltage. The case where the average of 6 sheets was 4.5 kV or more was evaluated as ◯, and the case where it was less than 4.5 kV was evaluated as ×. As a result, all of Examples 6-13 to 6-24 were ○, and all of Comparative Examples 6-5 to 6-8 were ×.
In addition, as an insulation reliability test, a DC voltage of 50 V was applied to each of six test pieces, a standing test was performed in an atmosphere of 130 ° C. and 85% RH, and the time until short-circuiting was measured. The case where the average of 6 sheets was 400 hours or more was evaluated as “◯”, and the case where it was less than 400 hours was evaluated as “X”. As a result, all of Examples 6-13 to 6-24 were ○, and all of Comparative Examples 6-5 to 6-8 were ×.

As described above in detail, it was confirmed that by using a printed wiring board material containing cellulose nanofibers manufactured from lignocellulose, improvement in withstand voltage and insulation reliability, which was impossible in the past, was achieved. .

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 13 Copper-clad laminate (test substrate)

13a Conductor layer

13b Insulating layer 14 Insulating resin layer 15 Laser via 16 Plating layer 17 Etching resist pattern 18 Wiring pattern 21 Copper-clad laminate (test substrate)

21a Conductor layer

21b Insulating layer 22 Insulating resin layer 23 Laser via 24 Plating layer 25 Etching resist pattern 26 Wiring pattern 27 Through hole 28 Through hole

Claims

A printed wiring board material comprising a binder component, cellulose nanofibers having a number average fiber diameter of 3 nm to 1000 nm, and an acrylic copolymer compound.
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.
The printed wiring board material according to claim 1, comprising layered silicate.
The printed wiring board material according to claim 1, comprising one or both of a silicone compound and a fluorine compound.
The printed wiring board material according to claim 1, wherein the cellulose nanofiber has a number average fiber diameter of 3 nm or more and less than 1000 nm, and further includes a cellulose fiber having a number average fiber diameter of 1 μm or more.
The printed wiring board material according to claim 1, wherein the cellulose nanofiber has a carboxylate in its structure.
The printed wiring board material according to claim 1, wherein the cellulose nanofiber is manufactured from lignocellulose.
The printed wiring board material according to claim 1, which is for solder resist.
2. The printed wiring board material according to claim 1, 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 any one of claims 1 to 10.