KR20160002810A - Printed-circuit-board material and printed circuit board using same - Google Patents

Abstract

The present invention provides a printed wiring board material which is less prone to smear on the surface of a metal foil such as copper and which is easy to remove even when it is formed, and a printed wiring board using the printed wiring board material. The printed wiring board material includes a binder component, a cellulose nanofiber having a number average fiber diameter of 3 nm to 1000 nm, and an acrylic copolymer compound, and can be suitably used for an interlayer insulating material for a solder resist and a multilayer printed wiring board. The printed wiring board uses this printed wiring board material.

Description

PRINTED CIRCUIT BOARD MATERIAL AND PRINTED CIRCUIT BOARD USING SAME [0002]

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

Examples of the wiring board such as a printed wiring board include a board in which a metal such as copper is adhered to a fiber such as glass impregnated with an epoxy resin or the like and a circuit is formed by an etching method, And a circuit is formed after the insulating layer is formed by laminating the insulating resin composition. Further, a solder resist is formed on the outermost layer of the wiring board for the purpose of protecting the circuit formed and mounting the electronic component in the correct position. As the solder resist, an insulating material such as an epoxy resin or an acrylate resin is generally used (for example, see Patent Documents 1, 2 and 3).

However, when a circuit is formed, a laser is used to form a hole (via) for interlayer connection, and there is a problem that a smear is likely to remain on the surface (via bottom) of the metal foil such as copper. If the desmear treatment is intensified to remove the smear on the via-bottom, since the insulating layer is eroded, it becomes difficult to fill the via-bottom and the inside of the via with plating (see, for example, Patent Document 4).

Further, the solder resist is partially removed to expose the circuit, and then the component is mounted by soldering or the like, or the wiring is taken out. A laser processing method in which a circuit is exposed by removing a solder resist in a desired portion by laser processing is used in addition to a photographic developing method using a photosensitive solder resist as a general method. However, in the laser processing method, there is a problem that smear (residue) tends to remain as in the case of forming a hole (via) for interlayer connection (see, for example, Patent Document 5).

Japanese Patent Application Laid-Open No. 2006-182991 (claims) Japanese Patent Laying-Open No. 2013-36042 (claims) Japanese Patent Application Laid-Open No. 08-269172 (claims and the like) Japanese Patent Application Laid-Open No. 2009-200301 (claims and the like) Japanese Patent Application Laid-Open No. 2010-031216 (claims, paragraphs [0079] to [0086], etc.)

An object of the present invention is to provide a printed wiring board material which is less prone to smear on the surface of a metal foil such as copper and which is easy to remove even when it is formed, and a printed wiring board using the same.

The present inventors have intensively studied and found that the above problems can be solved by using a material containing a cellulose nanofiber and an acrylic copolymer compound as a printed wiring board material, and have completed the present invention.

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

In the material for a printed wiring board of the present invention, as the binder component, a thermoplastic resin and a curable resin may be suitably used.

The printed wiring board material of the present invention preferably includes a layered silicate. The printed wiring board material of the present invention preferably contains either or both of a silicon compound and a fluorine compound. In the printed wiring board material of the present invention, it is preferable that the cellulose nanofibers further include a cellulose fiber having a number-average fiber diameter of 3 nm or more and less than 1000 nm and a number-average fiber diameter of 1 mu m or more.

In the printed wiring board material of the present invention, it is preferable that the cellulose nanofiber has a carboxylate in its structure. In the printed wiring board material of the present invention, it is preferable that the cellulose nanofiber is produced 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.

Further, the printed wiring board of the present invention is characterized by using the above-mentioned printed wiring board material of the present invention.

According to the present invention, by using a material containing a cellulose nanofiber and an acrylic copolymer compound as a material for a printed wiring board, it is possible to provide a printed wiring board material which is less prone to smear on the surface of a metal foil such as copper It becomes possible to realize a used printed wiring board.

1 is a partial cross-sectional view showing an example of the construction of a multilayer printed wiring board according to the present invention.
2 is an explanatory view showing a method for manufacturing a substrate for evaluation of smear removal performance of a solder resist and an interlayer insulating material in the embodiment.
3 is an explanatory diagram showing a method of manufacturing a substrate for evaluation of an interlayer insulating material in the embodiment.
4 is an explanatory diagram showing a method of manufacturing a substrate for evaluation of a core material in the embodiment.
5 is an explanatory view showing a method of manufacturing a substrate for evaluation of another core material in the embodiment.

DESCRIPTION OF THE PREFERRED EMBODIMENTS 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 by containing a binder component, a cellulose nanofiber having a number average fiber diameter of 3 nm to 1000 nm, and an acrylic copolymer compound. The cellulose nanofibers can be obtained as follows.

(Cellulose nanofibers having a number average fiber diameter of 3 nm to 1000 nm)

The cellulose nanofibers can be obtained as follows.

As the raw material of the cellulose nanofiber, pulp obtained from natural plant fiber raw materials such as wood or hemp, bamboo, cotton, jute, kenaf, bit, scum of agricultural products, cloth, and regenerated cellulose fiber such as rayon or cellophane can be used Of these, pulp is particularly suitable. Examples of the pulp include chemical pulp, semi-chemical pulp, semi-ground pulp, chemi-mechanical pulp, thermomechanical pulp, and chemi-thermo mechanical pulp, which are obtained by pulping a plant raw material chemically or mechanically, , Refiner mechanical pulp, sawdust pulp, and deinking pulp pulp based on these plant fibers, magazine pulp, corrugated cardboard pulp, and the like. Among them, various kinds of kraft pulp derived from softwoods having strong fiber strength, such as softwood bleached kraft pulp, softwood oxygen-exposed 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 therein is usually about 0 to 40 mass%, particularly about 0 to 10 mass%. With respect to these raw materials, the lignin amount can be adjusted by removing or bleaching lignin, if necessary. Further, the lignin content can be measured by the Klason method.

Among the cell walls of plants, cellulose molecules are not monomolecules but form microfibrils (cellulose nanofibers) having crystallinity in which dozens of aggregates regularly aggregate, and this is the basic skeleton material of plants. Therefore, in order to produce the cellulose nanofibers from the raw material, a method of loosening the fibers to nano-size can be used by subjecting the raw materials to high-temperature treatment, pulverization treatment, high-temperature high-pressure steam treatment, treatment with phosphate or the like.

The above-mentioned disintegrating and pulverizing treatment is a method of obtaining a cellulose nanofiber by directly applying a force to the raw material such as pulp and mechanically grinding or pulverizing the fiber to loosen the fiber. More specifically, for example, pulp or the like is mechanically treated with a high-pressure homogenizer or the like to prepare a water suspension of about 0.1 to 3 mass% of the cellulose fibers unwound at a fiber diameter of about 0.1 to 10 탆, Or the like to obtain a cellulose nanofiber having a fiber diameter of about 10 to 100 nm.

The above-mentioned grinding or grinding treatment can be carried out, for example, using a grinder " Pure Fine Mill " manufactured by Kurita Machine Works Co., This grinder is a millstone grinder for grinding a raw material with ultrafine particles by an impact, a centrifugal force and a shearing force generated when a raw material passes through a gap between two grinders in the upper and lower sides. The grinder is a millstone grinder for shearing, grinding, atomizing, Can be performed at the same time. The above grinding or firing treatment may also be carried out using a superfine grinding machine "Supermass Colloid" manufactured by Masuyuki Industries Co., The super mass colloid is a grinding machine that enables ultra-fine grinding to feel like melting beyond the area of simple grinding. The super-mass colloid is a mill-type granular grinding machine constituted by two upper and lower inorganic grindstones which can freely adjust the gap. The upper grindstone is fixed and the lower grindstone rotates at high speed. The raw material charged into the hopper is sent to the gap between the upper and lower grinding wheels by the centrifugal force, and the raw material gradually becomes shattered and becomes superfine by the strong compression, shearing and rolling friction force generated therefrom.

The high-temperature high-pressure steam treatment is a method of obtaining a cellulose nanofiber by exposing a raw material such as pulp to high-temperature high-pressure steam to loosen the fiber.

Further, the treatment with the phosphate or the like can be carried out in such a manner that the surface of the raw material such as pulp is phosphate-esterified to weaken the bonding force between the cellulose fibers, and then the refiner treatment (grinding or crushing treatment) It is a treatment method for obtaining a nanofiber. 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 infiltrated between cellulose fibers at 60 DEG C, After the reaction mixture was washed with water, it was subjected to a hydrolysis treatment at 60 ° C for 2 hours in a 3% by mass hydrochloric acid aqueous solution, followed by further washing with water. Thereafter, the resultant was further treated at a room temperature for 20 minutes in a 3% by mass aqueous sodium carbonate solution , The phosphorylation is completed, and the treated product is decomposed with a refiner (such as the above-mentioned grinder) to obtain a cellulose nanofiber.

The cellulose nanofibers used in the present invention may be chemically modified and / or physically modified to have enhanced functionality. Examples of the chemical modification include a method of adding a functional group by acetalization, acetylation, cyanoethylation, etherification, isocyanation or the like, compositing an inorganic material such as silicate or titanate by a chemical reaction, a sol-gel method, Or the like. As a method of chemical modification, for example, a method of immersing cellulose nanofiber formed into a sheet form in anhydrous acetic acid and heating can be mentioned. Examples of the physical modification method include a physical vapor deposition method (PVD method) such as vacuum deposition, ion plating and sputtering, a chemical vapor deposition method (CVD method), electroless plating or electrolytic plating Plating method or the like. These modifications may be carried out before or after the above-mentioned treatment.

The number average fiber diameter of the cellulose nanofibers 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 cellulose nanofiber staple fiber has a minimum diameter of 3 nm, less than 3 nm can not be substantially produced, and when it is more than 1000 nm, the dispersibility with the binder component deteriorates. The number average fiber diameter of the cellulose nanofibers can be measured by observing with a scanning electron microscope (SEM), a transmission electron microscope (TEM) or the like, drawing a line on the diagonal line of the photograph, The fibers are randomly extracted at 12 points, the largest and the thinnest fibers are removed, and the remaining 10 points are averaged.

The blending amount of the cellulose nanofibers used in the present invention is preferably from 0.1 to 80 mass%, more preferably from 0.2 to 70 mass%, based on the total amount of the composition excluding the solvent. When the blending amount of the cellulose nanofibers is 0.1 mass% or more, the desired effect of the present invention can be satisfactorily obtained. On the other hand, when the content is 80 mass% or less, film formability is improved.

Examples of the acrylic copolymer compound include poly (meth) acrylate and modified poly (meth) acrylate. Specific examples thereof include BYK-350, BYK-352 and BYK-354 manufactured by Big Chem Japan Co., , BYK-355, BYK-358N, BYK-358N, BYK-380N, BYK-381, BYK-392, BYK-394, BYK-3440, BYK-3550, BYK-SILCLEAN3700, Disperbyk-2000, Disperbyk OX-881, OX-883, OX-883HF, OX-77EF, OX-710, 1970, Disperbyk-2050, Disperbyk- LF-1982, LF-1983, LF-1984, LF-1985, Polyflow No. 7 manufactured by Kyoshi Kagaku Co., Ltd., 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, and the like, but the present invention is not limited thereto. These may be used alone or in combination of two or more.

The amount of the acrylic copolymer compound to be used in the invention is generally sufficient to be used, and is suitably 0.01 to 20 parts by mass, more preferably 0.01 to 10 parts by mass, per 100 parts by mass of the binder component, More preferably 0.05 to 3 parts by mass. When the amount of the acrylic copolymer compound is too small, there is a possibility that the desired effect of the present invention can not be obtained. When the amount is too large, so-called bleeding phenomenon occurs in which some liquid component of the acrylic copolymer compound in the cured product exudes to the surface of the cured product So that it is not preferable either.

(Binder component)

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

Examples of the thermoplastic resin include thermoplastic resins such as acrylic, modified acrylic, low density polyethylene, high density polyethylene, ethylene-vinyl acetate copolymer, polyethylene terephthalate, polypropylene, modified polypropylene, polystyrene, acrylonitrile-butadiene-styrene copolymer, acrylonitrile- Polyamide, thermoplastic polyurethane, polyacetal, polycarbonate, ultrahigh molecular weight polyethylene, polybutylene terephthalate, polyvinyl alcohol, polyvinyl alcohol, polyvinyl chloride, polyvinylidene chloride and polylactic acid, Polyamide 6T, polyamide 9T, polytetrafluoroethylene, polytetrafluoroethylene, polytetrafluoroethylene, polytetrafluoroethylene, polytetrafluoroethylene, polytetrafluoroethylene, polytetrafluoroethylene, phthalate, modified polyphenylene ether, polysulfone, polyphenylene sulfide, polyether sulfone, polyetheretherketone, polyallylate, polyetherimide, Fluoroethylene, polyvinylidene fluoride, poly Thermoplastic elastomers such as olefin-based, styrene-based, polyester-based, urethane-based, amide-based, vinyl chloride-based and hydrogenation-based thermoplastic elastomers.

As the thermosetting resin, any resin that is cured by heating and exhibits electrical insulation properties can be used. 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 type epoxy resins such as bisphenol P type epoxy resin and bisphenol Z type epoxy resin, bisphenol A novolak type epoxy resin, phenol novolak type epoxy resin and cresol novolac epoxy resin, biphenyl type epoxy resin, 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, phenoxy type epoxy resin, dicyclopentadiene type epoxy resin, norbornene type Epoxy resin, adamantane type epoxy resin, fluorene type epoxy resin, glycidyl Acrylate copolymer epoxy resin, copolymerized epoxy resin of cyclohexylmaleimide and glycidyl methacrylate, epoxy-modified polybutadiene rubber derivative, CTBN modified epoxy resin, trimethylolpropane polyglycidyl ether, phenyl-1, 3-diglycidyl ether, biphenyl-4,4'-diglycidyl ether, 1,6-hexanediol diglycidyl ether, diglycidyl ether of ethylene glycol or propylene glycol, sorbitol polyglycidyl (2-hydroxyethyl) isocyanurate, phenol novolak resin, cresol novolac resin, bisphenol A novolak resin, and the like can be used. Phenol resins, phenoxy resins, urea (urea) resins such as novolac phenol resins, unmodified resorphenol resins, and resorcinol phenol resins such as oil-modified resorphenol resins modified with tung oil, linseed oil,Butadiene resins, urea resins, urea resins, urea resins, urea resins, urea resins, urea resins, urea resins, urea resins, , Benzocyclobutene resin, maleimide resin, bismaleimide triazine resin, polyazomethine resin, and thermosetting polyimide.

As the radically polymerizable photo-curing resin, a resin which is cured by irradiation with an active energy ray to exhibit electric insulation property may be used, and in particular, a compound having at least one ethylenic unsaturated bond in the molecule is preferably used. As the compound having an ethylenically unsaturated bond, a photopolymerizable oligomer and a photopolymerizable vinyl monomer for publicly known generations are used.

Examples of the photopolymerizable oligomer include unsaturated polyester oligomers and (meth) acrylate oligomers. (Meth) acrylate oligomers include epoxy (meth) acrylates such as phenol novolac epoxy (meth) acrylate, cresol novolak epoxy (meth) acrylate and bisphenol epoxy Acrylate, epoxy urethane (meth) acrylate, polyester (meth) acrylate, polyether (meth) acrylate, and polybutadiene modified (meth) acrylate. Further, in the present specification, (meth) acrylate is a generic term for acrylate, methacrylate, and mixtures thereof, and the same applies to other similar expressions.

Examples of the photopolymerizable vinyl monomers include known ones such as styrene derivatives such as styrene, chlorostyrene and? -Methylstyrene; Vinyl esters such as vinyl acetate, vinyl butyrate and vinyl benzoate; N-butyl ether, vinyl-n-amyl ether, vinyl isoamyl ether, vinyl-n-octadecyl ether, vinyl cyclohexyl ether, ethylene glycol monobutyl vinyl ether Vinyl ethers such as ether and triethylene glycol monomethyl vinyl ether; Acrylamides such as acrylamide, methacrylamide, N-hydroxymethylacrylamide, N-hydroxymethylmethacrylamide, N-methoxymethylacrylamide, N-ethoxymethylacrylamide and N-butoxymethylacrylamide Meth) acrylamides; Allyl compounds such as triallyl isocyanurate, diallyl phthalate and diallyl isophthalate; (Meth) acrylate, pentaerythritol (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tetra Esters of (meth) acrylic acid such as acrylate; Hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and pentaerythritol tri (meth) acrylate; Alkoxyalkylene glycol mono (meth) acrylates such as methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate; Acrylates such as ethylene glycol di (meth) acrylate, butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolpropane tri , Alkylpolyol poly (meth) acrylates such as pentaerythritol tetra (meth) acrylate and dipentaerythritol hexa (meth) acrylate; Polyoxyalkylene glycol poly (meth) acrylates such as diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, ethoxylated trimethylolpropane triacrylate and propoxylated trimethylolpropane tri (meth) Meth) acrylates; Poly (meth) acrylates such as hydroxypivalic acid neopentyl glycol ester di (meth) acrylate; And isocyanurate type poly (meth) acrylates such as tris [(meth) acryloxyethyl] isocyanurate.

As the cationically polymerizable photo-curing resin, alicyclic epoxy compounds, oxetane compounds and vinyl ether compounds can be suitably used. Examples of the alicyclic epoxy compound include 3,4,3 ', 4'-diepoxybicyclohexyl, 2,2-bis (3,4-epoxycyclohexyl) propane, 2,2- Bis (3,4-epoxycyclohexyl) ethylbenzene, bis (3,4-epoxycyclohexyl) methane, 1- [ Epoxycyclohexyl) adipate, 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate, (3,4-epoxy-6-methylcyclohexyl) methyl- Epoxy-6-methylcyclohexanecarboxylate, ethylene-1,2-bis (3,4-epoxycyclohexanecarboxylic acid) ester, cyclohexenesoxide, 3,4-epoxycyclohexylmethyl alcohol, And alicyclic epoxy compounds having an epoxy group such as 4-epoxycyclohexylethyltrimethoxysilane. Examples of commercially available products include Celllock 2000, Celllock 2021, Celllock 3000, EHPE 3150; Epomic VG-3101 manufactured by Mitsui Chemicals, Inc.; E-1031S manufactured by Mitsubishi Chemical Corporation; TETRAD-X and TETRAD-C manufactured by Mitsubishi Gas Chemical Company; EPB-13 and EPB-27 manufactured by Nippon Soda Co., Ltd., and the like.

Examples of the oxetane compound include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [ Methyl-3-oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3-ethyl-3-oxetanyl) methyl methacrylate, (3-methyl-3-oxetanyl) methyl methacrylate, Or polyfunctional oxetanes such as polytetrafluoroethylene, polytetrafluoroethylene, polytetrafluoroethylene, polytetrafluoroethylene, polytetrafluoroethylene, polytetrafluoroethylene, polytetrafluoroethylene, polytetrafluoroethylene, And oxetane compounds such as a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth) acrylate. As commercial products, for example, ether cocatalyst OXBP, OXMA, OXBP, EHO, xylylene bisoxetane manufactured by Ube Gosan Co., Ltd., alon oxetane OXT-101, OXT-201, OXT- 211, OXT-221, OXT-212, OXT-610, and PNOX-1009.

Examples of the vinyl ether compound include cyclic ether vinyl ethers such as isobornyl divinyl ether and oxanorbornene divinyl ether (vinyl ether having a cyclic ether group such as oxirane ring, oxetanyl ring and oxolane ring); Aryl vinyl ethers such as phenyl vinyl ether; alkyl vinyl ethers such as n-butyl vinyl ether and 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, and the like having a substituent such as an alkyl group or an allyl group at the? And / Vinyl ether compounds and the like. Examples of commercially available products include 2-hydroxyethyl vinyl ether (HEVE), diethylene glycol monovinyl ether (DEGV), 2-hydroxybutyl vinyl ether (HBVE), tri Ethylene glycol divinyl ether, and the like.

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

(Carboxyl group-containing resin)

As the carboxyl group-containing resin, both 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, and the present invention is not limited thereto. As the carboxyl group-containing resin, resins listed below can be suitably used.

(1) a carboxyl group-containing resin obtained by copolymerization of a compound having an unsaturated carboxylic acid and an unsaturated double bond, and a carboxyl group-containing resin obtained by modifying the molecular weight and acid value thereof.

(2) A photosensitive carboxyl-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) reacting an unsaturated monocarboxylic acid with a copolymer of a compound having an epoxy group and an unsaturated double bond each in a molecule and a compound having an unsaturated double bond, and reacting the unsaturated monocarboxylic acid with a second class of hydroxyl groups A photosensitive carboxyl group-containing resin obtained by reacting a saturated or unsaturated polybasic acid anhydride.

(4) a method of reacting a hydroxyl group-containing polymer with a saturated or unsaturated polybasic acid anhydride, and then reacting the resulting carboxylic acid with a compound having one epoxy group and one unsaturated double bond in each molecule to form a photosensitive hydroxyl group and a carboxyl group Containing resin.

(5) A photosensitive carboxyl-containing resin obtained by reacting a polyfunctional epoxy compound with an unsaturated monocarboxylic acid, and reacting a part or all of the hydroxyl groups of the second grade produced by the reaction with a polybasic acid anhydride.

(6) A process for producing a polyfunctional epoxy compound, which comprises reacting a polyfunctional epoxy compound and a compound having one reactor other than a hydroxyl group reacting with at least two hydroxyl and epoxy groups in a molecule, with a monocarboxylic acid containing an unsaturated group, To obtain a carboxyl group-containing photosensitive resin.

(7) A carboxyl group-containing photosensitive resin obtained by reacting a reaction product of a resin having a phenolic hydroxyl group with an alkylene oxide or cyclic carbonate with an unsaturated group-containing monocarboxylic acid, and reacting the obtained reaction product with a polybasic acid anhydride.

(8) A process for producing a polyfunctional epoxy compound, which comprises reacting a polyfunctional epoxy compound, a compound having at least one alcoholic hydroxyl group and at least one phenolic hydroxyl group in a molecule with an unsaturated group-containing monocarboxylic acid, and reacting the alcoholic hydroxyl group of the obtained reaction product with a polybasic acid anhydride A carboxyl group-containing photosensitive resin obtained by reacting an anhydride group.

In addition to the cellulose nanofibers, the binder component, and the acrylic copolymer compound, the printed wiring board material of the present invention can appropriately blend other blending ingredients for public use depending on the use thereof.

Examples of other blending components for general use include a curing catalyst, a photopolymerization initiator, a colorant, and an organic solvent.

The curing catalyst is for curing a thermosetting resin mainly in the curable resin and includes, for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl- Imidazole derivatives such as phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole and 1- (2-cyanoethyl) ; Amines such as dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine and 4- Compounds, hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; And phosphorus compounds such as triphenylphosphine. U-CAT3503N, U-CAT3502T, DBU, DBN, U-CATSA102, U-CATSA102, and U-CATSA102 are commercially available products such as 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ and 2P4MHZ (manufactured by Shikoku Chemicals Corporation) CAT5002 (manufactured by SAN-APRO CO., LTD.), And the like, or a mixture of two or more of them may be used. Likewise, it is also possible to use, for example, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2- Triazine, isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, isocyanuric acid, S-triazine derivatives such as acid adducts may also be used.

The photopolymerization initiator is for curing the photocurable resin in the curable resin and includes, for example, benzoin such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin alkyl ethers ; Acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, etc. Acetophenones; 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane- Aminoalkylphenones such as 1, 2- (dimethylamino) -2 - [(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone; Anthraquinones such as 2-methyl anthraquinone, 2-ethyl anthraquinone, 2-tert-butyl anthraquinone, and 1-chloro anthraquinone; Thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone and 2,4-diisopropylthioxanthone; Ketal 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-trimethylbenzoyldiphenylphosphine oxide Phosphine oxides such as ethylidene-2,4,6-trimethylbenzoyl phenylphosphinate; Various peroxides, titanocene initiators, and the like. These include photoinitiators such as tertiary amines such as N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylaminobenzoate, triethylamine and triethanolamine Or may be used in combination. These photopolymerization initiators may be used alone or in combination of two or more.

As the coloring agent, known coloring pigments, dyes and the like represented by a color index 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 , Pigment Green 7, 36, 3, 5, 20, 28, Solvent Yellow 163, Pigment Yellow (Pigment Yellow), 83, 87, 94, 97, 122, 136, ) 24, 108, 193, 147, 199, 202, 110, 109, 139, 179, 185, 93, 94, 95, 128, 155, 166, 180, 120, 151, 154, 156, 175, 181, 1 , 2, 3, 4, 5, 6, 9, 10, 12, 61, 62, 62: 1, 65, 73, 74, 75, 97, 100, 104, 105, 111, 116, 167, 168, 169 182, 183, 12, 13, 14, 16, 17, 55, 63, 81, 83, 87, 126, 127, 152, 170, 172, 174, 176, 188, 198, Pigment Orange, 1, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 61, 63, 64, 71, 73, Pigment Red 1, 2 , 3, 4, 5, 6, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 112, 114, 146, 147, 151, 170, 184, 187, 188 48: 3, 48: 4, 49: 1, 49: 2, 50, 50, 50, : 1, 52: 1, 52: 2, 53: 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 , Solvent Red 135, 179 (Solvent Red), 254, 255, 264, 270, 272, 220, 144, 166, 214, 220, 221, 242, 168, 177, 216, 122, 202, , 149, 150, 52, 207, Pigment Violet 19, 23, 29, 32, 36, 38, 42, Solvent Violet 13, 36, Pigment Brown 23, 25 , Pigment Black 1 and 7, and the like.

Examples of the organic solvent 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 monoethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monoethyl ether, etc. Of glycol ethers; Esters such as ethyl acetate, butyl acetate, cellosolve acetate, diethylene glycol monoethyl ether acetate and esters of the glycol ethers; Alcohols such as ethanol, propanol, ethylene glycol and propylene glycol; Aliphatic hydrocarbons such as octane and decane; Petroleum ether such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha and solvent naphtha.

If necessary, additives such as a vesicle / leveling agent, a thixotropic agent / thickener, a coupling agent, a dispersant, and a flame retardant may be contained.

Examples of the antifoaming agents and leveling agents include silicones, modified silicones, mineral oils, vegetable oils, aliphatic alcohols, fatty acids, metal soaps, fatty acid amides, polyoxyalkylene glycols, polyoxyalkylene alkyl ethers, Can be used.

Examples of the thixotropic agent and thickener include clay minerals such as kaolinite, smectite, montmorillonite, bentonite, talc, mica and zeolite, fine silica, silica gel, amorphous inorganic particles, polyamide-based additives, modified urea-based additives, Can be used.

Examples of the coupling agent include a methoxy group, an ethoxy group and an acetyl group as an alkoxy group and the reactive functional groups include vinyl, methacryl, acrylic, epoxy, cyclic epoxy, mercapto, amino, diamino, acid anhydride, ureido, sulfide, , Vinyl-based silane compounds such as vinyl ethoxysilane, vinyltrimethoxysilane, vinyl tris (? -Methoxyethoxy) silane and? -Methacryloxypropyltrimethoxysilane,? -Aminopropyl (Aminoethyl)? - aminopropylmethyldimethoxysilane,? - ureidopropyltriethoxysilane, and the like can be used as the silane coupling agent, such as trimethoxysilane, N-β- (aminoethyl) γ-aminopropyltrimethoxysilane, Epoxy silane compounds such as amino silane compounds,? - glycidoxypropyltrimethoxysilane,? - (3,4-epoxycyclohexyl) ethyltrimethoxysilane and? -Glycidoxypropylmethyldiethoxysilane, such as? -mercaptopropyltrimethoxysilane Silane coupling agents such as mercapto silane compounds and phenylamino silane compounds such as N-phenyl-gamma -aminopropyltrimethoxysilane, isopropyl triisostearoyl titanate, tetraoctyl bis (ditridecyl phosphite) (Dioctyl pyrophosphate) oxyacetate titanate, isopropyltridodecylbenzene sulfonyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, tetraisopropyl bis (dioctylphosphite) (Ditridecylphosphate) ethylene titanate, isopropyltri octanoyl titanate, isopropyl tin octanoate titanate, tetra (1,1-diallyloxymethyl-1-butyl) Isopropyltrimethacrylate, isopropyltrimethacrylate, isopropyldimethacrylate, isostearyl acrylate, isopropyldimethacrylate, isostearyl acrylate, isopropyltrimethacrylate, isopropyltrimethacrylate, Titanate-based coupling agents such as phenyltrimethylammonium phenyl titanate, dicumylphenyloxyacetate titanate and diisostearoylethylenetitanate, ethylenically unsaturated zirconate-containing compounds, neoalkoxyzirconate-containing compounds, neoalkoxy (Dioctyl) phosphate zirconate, neoalkoxytris (dioctyl) pyrophosphate zirconate, neoalkoxytris (dodecyl) benzenesulfonylate, neoalkoxytris (2,2-diallyloxymethyl) butyl, di (ditridecyl) phosphitol zirconate, neopentyl (ethylenediamino) ethyl zirconate, neoalkoxytris (Diallyl) oxy, trienodecanoyl zirconate, neopentyl (diallyl) oxy, tri (dodecyl) benzene-sulfonyl zirconate, neopentyl Dioctyl) phosphatozirconate, neopentyl (diallyl) oxy, tri (N-ethylenediamino) ethylzirconate, , Neopentyl (diallyl) oxy, tri (m-amino) phenylzirconate, neopentyl (diallyl) oxy, trimethacrylic zirconate, neopentyl Di (3-mercapto) propionic zirconate, zirconium (IV) 2,2-bis (2-naphthyl) Propionolate methyl) butanolate, cyclodi [2,2- (bis 2-propanolate methyl) butanolate] zirconate coupling agents such as pyrophosphato-O and O, diisobutyl An aluminate-based coupling agent such as acetoacetyl aluminate and alkyl acetoacetate aluminum diisopropylate may be used The.

Examples of the dispersing agent include polymer dispersing agents such as polycarboxylic acid type, naphthalenesulfonic acid formalin condensation type, polyethylene glycol, polycarboxylic acid partial alkyl ester type, polyether type, and polyalkylene polyamine type, alkylsulfonic acid type, quaternary ammonium type, Molecular-weight dispersants such as higher alcohol alkylene oxide-based, polyhydric alcohol ester-based, alkylpolyamine-based, and the like.

Examples of the flame retardant include metal hydroxides such as aluminum hydroxide and magnesium hydroxide, ammonia, ammonium phosphate, ammonium carbonate, zinc borate, zinc stannate, molybdenum compound, bromine compound, chlorine compound, phosphoric acid ester, phosphorus- Melamine cyanurate, melamine compound, triazine compound, guanidine compound, silicone polymer and the like can be used.

Examples of the other compounding ingredients include photoacid generators such as diazonium salts, sulfonium salts and iodonium salts, photobase generators such as carbamate compounds,? -Amino ketone compounds and O-acyloxime compounds, barium sulfate, spherical silica , Inorganic fillers such as hydrotalcite, organic fillers such as silicone powder, nylon powder and fluorine powder, radical scavengers, ultraviolet absorbers, peroxide dissolution inhibitors, thermal polymerization inhibitors, adhesion promoters and rust inhibitors.

The printed wiring board material according to the present invention having such a constitution as described above can be suitably applied to solder resists and can be suitably used for an interlayer insulating material of a multilayer printed wiring board. Thus, in the obtained printed wiring board, The desired effect of the present invention can be obtained. When the present invention is applied to a printed wiring board material, a method of forming the cellulose nanofibers into a sheet, impregnating the sheet-like cellulose nanofibers with a binder component, and drying the prepregs may be used .

1 is a partial cross-sectional view showing an example of the construction of a multilayered printed circuit board according to the present invention. The multilayer printed circuit board shown in the drawing 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 formation of the through hole can be performed by a suitable means such as a drill, a die punch, or a laser beam. Thereafter, the roughening treatment is performed using a roughening agent. In general, the roughening treatment is carried out by swelling 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 soda, , Permanganate, ozone, hydrogen peroxide / sulfuric acid, and nitric acid.

Subsequently, the conductor pattern 3 is formed by a combination of electroless plating and electrolytic plating. The step of forming the conductive layer by electroless plating is a step of immersing the conductive layer in an aqueous solution containing a plating catalyst to adsorb the catalyst, and immersing the plating solution in the plating solution to precipitate 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 conductor patterns 3 are formed on both sides . 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 to each other, A hole 5 is formed.

Then, the thermosetting composition is applied, for example, by an appropriate method such as a screen printing method, a spray coating method, or a curtain coating method, followed by heating and curing to form an interlayer insulating layer 6. When a dry film or a prepreg is used, it is laminated or hot plate pressed and heat-cured to form an interlayer insulating layer 6. Next, the vias 7 for electrically connecting the connection portions of the respective conductor layers are formed by suitable means such as laser light, and the conductor patterns 8 are formed in the same manner as the conductor patterns 3 . Further, the interlayer insulating layer 9, the vias 10 and the conductor pattern 11 are formed in the same manner. Thereafter, a solder resist layer 12 is formed on the outermost layer, whereby a multilayer printed wiring board is produced. In the above, an example in which the interlayer insulating layer and the conductor layer are formed on the laminated substrate has been described. However, a single-sided substrate or a double-sided substrate may be used instead of the laminated substrate.

The printed wiring board material of the present invention preferably further comprises a layered silicate. By combining the cellulose nanofibers in combination with the layered silicate, the coefficient of linear expansion can be remarkably reduced by a smaller amount than in the case where any one is blended.

The layer silicate is not particularly limited, but a clay mineral or a hydrotalcite compound having swelling property and / or wall property and a similar compound are preferable. Examples of these clay minerals include kaolinite, dickite, nacrite, halite, antigorite, creosotile, pyrophyllite, montmorillonite, bederite, nontronite, saponite, Site, hectorite, squid mica, sodium teniolite, muscovite, margarite, talc, vermiculite, phlogopite, janopilite, chlorite and the like. These layered silicates may be natural or synthetic. These layered silicates may be used singly or in combination.

The shape of the layered silicate is not particularly limited, but if the layered silicate is overlapped in multiple layers, it becomes difficult to cleave after organicization, so the thickness of the layered silicate that has not been converted to a mineral oil is preferably as thick as one layer About 1 nm). The average length is preferably 0.01 to 50 탆, more preferably 0.05 to 10 탆, and the aspect ratio is 20 to 500, preferably 50 to 200.

The layered silicate has ion exchangeable inorganic cations between its layers. The ion-exchangeable inorganic cation refers to a metal ion such as sodium, potassium or lithium existing on the crystal surface of the layer silicate. These ions can be intercalated (intercalated) between the layers of the layered silicate by having various materials having ionic exchange with the cationic material and having cationicity by ion exchange reaction.

The cation exchange capacity (CEC) of the layer silicate is not particularly limited, but is preferably 25 to 200 meq / 100 g, more preferably 50 to 150 meq / 100 g, further preferably 90 to 130 meq / 100 g Do. When the cation exchange capacity of the layer silicate is 25 meq / 100 g or more, a sufficient amount of cationic material is intercalated (intercalated) between the layers of the layer silicate by ion exchange, so that the interlayer is sufficiently hydrophilic. On the other hand, when the cation exchange capacity is 200 meq / 100 g or less, the interlayer bonding force of the layered silicate becomes too strong, so that the thin flakes do not easily peel off and the good dispersibility can be maintained.

Specific examples of the layer silicate satisfying the above-mentioned preferable conditions include Sumekuton SA manufactured by Kunimine Kogyo Co., Ltd., Gunipia F manufactured by Kunimine Kogyo Co., Ltd., SOMASIF ME- 100, Lucentite STN manufactured by Kobunshi Kagaku Co., Ltd., and the like.

As the organizing agent of the layer silicate used in the present invention, any ordinary onium salt may be used, and from the viewpoint of heat resistance, an onium salt having a high thermal decomposition temperature as disclosed in Japanese Patent Application Laid-Open No. 2004-107541 Is preferably used.

The method of incorporating the organic hydrophilicizing agent between the layers of the layered silicate is not particularly limited, but from the viewpoint of easiness of the synthesis, a method of containing the inorganic cation by exchanging the inorganic cation with the organic hydrophilicizing agent by ion exchange reaction is suitable. The method of ion-exchanging the ion-exchangeable inorganic cations of the layer silicate with the organic hydrophilicizing agent is not particularly limited, and a known method can be used. Specifically, ion exchange in water, ion exchange in alcohol, and ion exchange in a water / alcohol mixed solvent can be used.

Concretely, the layered silicate is sufficiently solvated with water or alcohol, and then a lubricating agent is added and stirred to replace inorganic cations between the layers of the layered silicate with a hydrophilizing agent. Thereafter, the unsubstituted lipophilic agent is thoroughly washed, filtered off and dried. Alternatively, the layer silicate and the organic cation may be directly reacted in an organic solvent, or the layer silicate and the hydrophilicizing agent may be reacted while being heated and kneaded in an extruder in the presence of a resin or the like.

The progress of the ion exchange can be confirmed by a known method. For example, there are a method of confirming the inorganic ions exchanged by the ICP emission analysis of the filtrate, a method of confirming that the layer spacing of the layer silicate is expanded by X-ray analysis, It can be confirmed that inorganic cations of the layer silicate are replaced with a hydrophilizing agent by a method of confirming the presence of a lipophilic agent. The ion exchange is preferably 0.05 equivalent (5 mass%) or more, more preferably 0.1 equivalent (10 mass%) or more, and 0.5 equivalent (50 mass%) or more based on 1 equivalent of the ion exchangeable inorganic ion of the layer silicate More preferable. The ion exchange is preferably carried out at a temperature of 0 to 100 캜, more preferably at a temperature of 10 to 90 캜, and more preferably at a temperature of 15 to 80 캜.

The compounding amount of the layer silicate used in the present invention is preferably 0.02 to 48 mass%, more preferably 0.04 to 42 mass%, based on the total amount of the composition excluding the solvent. When the compounding amount of the layer silicate is 0.02 mass% or more, the effect of reducing the linear expansion coefficient can be satisfactorily obtained. On the other hand, when the content is 48% by mass or less, film formability is improved.

According to the present invention, by combining the cellulose nanofibers and the layered silicate in combination, it is possible to obtain a material in which the coefficient of linear expansion is greatly reduced by a smaller amount than in the case where either one is blended due to the synergistic effect. The total amount of the cellulose nanofibers and the layered silicate in the present invention is preferably 0.1 to 80 mass%, more preferably 0.2 to 70 mass%, based on the total amount of the composition excluding the solvent.

The printed wiring board material of the present invention preferably contains either or both of a silicon compound and a fluorine compound. By containing either or both of a silicone compound and a fluorine compound, it becomes possible to obtain an effect of suppressing the occurrence of hallograft migration.

(Silicon compound)

As the silicone compound, there may be mentioned, for example, polydimethylsiloxane, polyalkylphenylsiloxane, alkyl modified silicone oil, polyether modified silicone oil, polyalkylsiloxane, polymethylsilsesquioxane, polyalkylhydrogensiloxane, polyalkylalkenylsiloxane, polymethylphenylsiloxane , Aralkyl-modified silicone oil, alkylaralkyl-modified silicone oil, and the like. Commercial products include BYK-300, BYK-302, BYK-306, BYK-307, BYK-310, BYK-313, BYK-330, BYK-331, BYK- KS-69, FZ-2110, FZ-2166, FZ-2154, FZ-2120, L-720 and L-7002 (trade names, BYK-370 and BYK375 manufactured by Big Chemie Japan K.K. KF-353, KF-615A, KF (trade name, manufactured by Dow Corning Toray Co., Ltd.), FZ- 640, KF-642, KF-643, KF-6020, X-22-6191, KF-6011, KF-6015, X-22-2516, KF-410, X-22-821, KF- -413 and KF-4701 (all manufactured by Shin-Etsu Chemical Co., Ltd.).

(Fluorine compound)

Examples of the fluorine compound include a fluorine-based resin having a perfluoroalkyl group, a perfluoroalkenyl group, or the like in the molecule. Examples of commercially available products include Megaface F-444, Dong F-472, Dong F-477, Dong F-552, Dong F-553, Dong F-554, Dong F-443, Dong F- 470, F-475, F-482, F-483, F-489, R-30 and RS-75 (manufactured by DIC Corporation), F-top EF301, (Available from Shin-Akita Kasei Co., Ltd.), Florad FC-430, FC-431 (manufactured by Sumitomo 3M Limited), Asahi Guard AG-E300D, Surplon S- (Manufactured by Asahi Glass Co., Ltd.), BM-1000, BM-1100 (manufactured by Asahi Kasei Corporation), SC-102, SC-103, SC- ), NBX-15 and FTX-218 (manufactured by Neos Co., Ltd.).

The amount of the silicone compound and / or the fluorine compound to be used in the present invention is preferably 0.01 to 20 parts by mass, more preferably 0.01 to 10 parts by mass, more preferably 0.01 to 10 parts by mass, per 100 parts by mass of the binder component, 0.05 to 3 parts by mass. When the blending amount of the silicone compound and / or the fluorine compound is 0.01 mass% or more, the desired effect of the present invention can be satisfactorily obtained. On the other hand, when it is 20 mass% or less, film formability is improved.

The printed wiring board material of the present invention preferably comprises a cellulose fiber having a number average diameter of at least 1 mu m and a cellulose nanofiber having a number average diameter of at least 3 nm and less than 1000 nm. By combining cellulose fibers having different fiber diameters in combination, it becomes possible to realize a high peel strength as compared with the conventional one.

(Cellulose fiber)

The above-mentioned cellulose fibers can be obtained as follows.

Examples of raw materials for the cellulose fibers include the same ones as the above-mentioned cellulose nanofibers.

In order to produce the cellulose fiber from the raw material, a method in which the raw material is subjected to beating or grinding treatment may be used.

In the above-mentioned compaction and pulverization treatment, for example, pulp or the like is mechanically treated with a high-pressure homogenizer or the like to obtain a cellulose fiber as a water suspension having a fiber diameter of about 1 to 10 탆 and about 0.1 to 3 mass% .

Further, for example, cellulose nanofibers having a fiber diameter of about 10 to 100 nm can be obtained by repeatedly loosening the cellulose fibers obtained by the digestion or grinding treatment with a grinder or the like.

In addition, the cellulose fiber used in the present invention may be one that is chemically modified and / or physically modified in the same manner as the above-mentioned cellulose nanofiber, thereby enhancing the functionality.

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

The number-average fiber diameter of the cellulose fibers is required to be 1 占 퐉 or more, preferably 1 占 퐉 to 50 占 퐉, and more preferably 1 占 퐉 to 20 占 퐉. If the number average fiber diameter of the cellulose fibers is smaller than the above range, the desired effect can not be obtained.

In the present invention, when the fibers are released to the nano-size in the process of manufacturing the cellulose nanofibers, the treatment is stopped in the middle and the entire amount is not released, thereby leaving the cellulose fibers in the range of the number- , A mixture of a cellulose fiber and a cellulose nanofiber satisfying the preferable conditions of the present invention can be obtained. Therefore, in the printed wiring board material of the present invention, in addition to the cellulose fibers and the cellulose nanofibers satisfying the specific number average fiber diameter range, cellulose fibers having a number average fiber diameter outside the specific number average fiber diameter range .

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

According to the present invention, by combining the cellulose fibers and the cellulose nanofibers in combination, excellent peel strength can be realized without conventionally. The mass ratio of the cellulose fibers to the cellulose nanofibers in the present invention is suitably from 9: 1 to 1: 9, more preferably from 8: 2 to 2: 8. Within this range, a higher peel strength can be obtained.

In this case, the total amount of the cellulose fibers and the cellulose nanofibers to be blended is preferably 0.5 to 80% by mass, more preferably 1 to 70% by mass, based on the total amount of the composition excluding the solvent. By setting the total amount of the cellulose fibers and the cellulose nanofibers to 0.5 mass% or more, a higher peel strength can be obtained, and when the total amount of the cellulose fibers and the cellulose nanofibers is 80 mass% or less, good film formability can be obtained.

The printed wiring board material of the present invention preferably includes a cellulose nanofiber having a carboxyl group-containing structure and a number average fiber diameter of 3 nm to 1000 nm. As a result, a printed wiring board material excellent in crack resistance can be obtained. Such a cellulose nanofiber can be obtained by oxidizing a natural cellulose fiber and then refining it according to the following.

(Cellulose nanofiber having a carboxylate in the structure)

First, an aqueous dispersion is prepared by dispersing natural cellulose fibers in water of about 10 to 1000 times (on a mass basis) basis on an absolute drying basis using a mixer or the like. Examples of the natural cellulose fibers to be used as raw materials of the cellulose nanofibers include wood pulp such as softwood pulp and hardwood pulp, non-wood pulp such as barley pulp and bagasse pulp, surface pulp such as cotton lint and cotton linter, Bacterial cellulose and the like. These may be used singly or in combination of two or more kinds. Further, these natural cellulose fibers may be subjected to treatment such as beating in order to increase the surface area in advance.

Then, in the aqueous dispersion, an oxidation treatment of the natural cellulose fibers is carried out using an N-oxyl compound as an oxidation catalyst. Examples of such N-oxyl compounds include 4-carboxy-TEMPO, 4-acetamido-TEMPO, 4-amino-TEMPO , 4-dimethylamino-TEMPO, 4-phosphonoxy-TEMPO, 4-hydroxy TEMPO, 4-oxy TEMPO, 4-methoxy TEMPO, 4- (2-bromoacetamide) But it is possible to use TEMPO derivatives having various functional groups at the C4 position, such as N-oxyl, and the like. The amount of these N-oxyl compounds to be added is sufficient as a catalytic amount, and may be in the range of 0.1 to 10% by mass on the basis of absolute drying on natural cellulose fibers.

In the oxidation treatment of the natural cellulose fibers, an oxidizing agent and a co-oxidizing agent are used in combination. Examples of the oxidizing agent include, for example, an alkali metal halide such as an alkali metal halide such as sodium hypochlorite and sodium hypochlorite, Suitable. As the co-oxidizing agent, 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 mass% based on the absolute dry basis with respect to the natural cellulose fiber, and the amount of the co-oxidizing agent used is usually about 1 to 30 mass% Range.

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 advancing the oxidation reaction. The temperature of the aqueous dispersion during the oxidation treatment can be arbitrarily set in the range of 1 to 50 占 폚, and it can be reacted at room temperature without temperature control. The reaction time may be in the range of 1 to 240 minutes. In addition, a penetrating agent may be added to the aqueous dispersion to penetrate the drug into the interior of the natural cellulose fiber and introduce more carboxyl groups to the fiber surface. Examples of the penetrating agent include anionic surfactants such as carboxylic acid salts, sulfuric acid ester salts, sulfonic acid salts and phosphoric acid ester salts, and nonionic surfactants such as polyethylene glycol type and polyhydric alcohol type.

After the oxidation treatment of the natural cellulose fibers, it is preferable to carry out a purification treatment for removing impurities such as unreacted oxidizing agents and various by-products contained in the aqueous dispersion before fineness. Specifically, for example, a method of repeatedly washing and washing the oxidized natural cellulose fiber can be used. The natural cellulose fiber obtained after the purification treatment is usually provided in the fineness treatment in a state in which an appropriate amount of water is impregnated. If necessary, the cellulose fiber may be subjected to a drying treatment to be formed into a fibrous or powdery form.

Subsequently, the fineness of the natural cellulose treatment is carried out in a state in which the natural cellulose fibers that have been subjected to purification treatment as desired are dispersed in a solvent such as water. The solvent used as the dispersion medium used in the micronization treatment is usually water, but it is preferable to use water as the solvent. The solvent may be an alcohol (such as methanol, ethanol, isopropanol, isobutanol, sec-butanol, (Acetone, methyl ethyl ketone, N, N-dimethylformamide, N, N-dimethylformamide and the like), ethers (ethylene glycol dimethyl ether, 1,4-dioxane and tetrahydrofuran) Dimethylacetamide, dimethylsulfoxide, etc.) and the like, or a mixture thereof may be used. The solid content concentration of the natural cellulose fibers in the dispersion of these solvents is suitably 50 mass% or less. When the solid content concentration of the natural cellulose fiber exceeds 50 mass%, it is not preferable because a very high energy is required for dispersion. The fineness of the natural cellulose treatment can be controlled by dispersing the dispersion in a low pressure homogenizer, a high pressure homogenizer, a grinder, a cutter mill, a ball mill, a jet mill, a beaker, a grinder, a single screw extruder, a twin screw extruder, an ultrasonic stirrer, Device can be used.

The cellulose nanofibers obtained by the micronization treatment may be, if desired, in the form of a suspension liquid in which the solid content concentration is adjusted or in the form of a dried powder. Here, in the case of the suspension liquid phase, only water may be used as the dispersion medium, or a mixed solvent of water and another organic solvent, for example, an alcohol such as ethanol, a surfactant, an acid, or a base may be used.

The hydroxyl group at the C6 position of the constituent 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 to 3 mmol / g by the oxidation treatment and the fineness treatment of the natural cellulose fiber The cellulose nanofibers of high crystallinity having the predetermined number average fiber diameter can be obtained. This highly-crystalline cellulose nanofiber has a cellulose I-form crystal structure. This means that such a cellulose nanofiber is a surface-oxidized microfine cellulose-derived molecule having an I-form crystal structure. That is, in the natural cellulose fiber, fine fibers called microfibrils produced in the process of biosynthesis thereof are multi-bundled to form a high-order solid structure, and the strong cohesive force between the microfibrils ) Is weakened by the introduction of an aldehyde group or a carboxyl group by an oxidation treatment, and further subjected to a fineness treatment to obtain a cellulose nanofiber. By controlling the conditions of the oxidation treatment, the average fiber diameter, the average fiber length, the average aspect ratio and the like of the cellulose nanofiber can be controlled by varying the polarity by changing the content of the carboxyl group or by the electrostatic repulsion or refinement treatment of the carboxyl group have.

The fact that the natural cellulose fiber has an I-form crystal structure means that in a diffraction profile obtained by measurement in the wide angle X-ray diffraction pattern thereof, a typical peak at two positions near 2? = 14 to 17 占 and 2? = 22 to 23 占It can be identified because it has. The reason that the carboxyl group is introduced into the cellulose molecules of the cellulose nanofiber is that the absorption due to the carbonyl group (around 1608 cm ^-1 ) in the total absorption infrared spectroscopy (ATR) exists in the sample in which moisture is completely removed have. In the case of the carboxyl group (COOH), absorption was observed at 1730 cm ^-1 in the above measurement.

In addition, since halogen atoms are attached or bonded to the natural cellulose fibers after the oxidation treatment, dehalogenation treatment may 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.

Concretely, for example, natural cellulose fibers after oxidation treatment are mixed with 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 about 1:10 to 1:60 (by mass ratio) Lt; / RTI > The concentration of the hydrogen peroxide solution in this case is suitably 1 to 50 g / L, more preferably 5 to 20 g / L. In addition, the pH of the hydrogen peroxide solution is suitably from 8 to 11, more preferably from 9.5 to 10.7.

The amount of the carboxyl group in the cellulose [mmol / g] with respect to the weight of the cellulose nanofiber contained in the aqueous dispersion can be evaluated by the following method. That is, 60 ml of a 0.5 to 1 mass% aqueous dispersion of a cellulose nanofiber sample having a dry weight determined in advance was prepared, and the pH was adjusted to about 2.5 with a 0.1 M hydrochloric acid aqueous solution. Thereafter, a 0.05 M aqueous sodium hydroxide solution 11, and the electrical conductivity is measured. From the amount of sodium hydroxide (V) consumed in the neutralization step of the weak acid in which the change in the electric conductivity is gentle, the amount of the functional group can be determined using the following formula. This amount of functional group indicates the amount of carboxyl group.

Functional group amount [mmol / g] = V [ml] x 0.05 / cellulose nanofiber sample [g]

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

In this case, the blending amount of the cellulose nanofibers having a carboxylate salt in the structure of the printed wiring board material is preferably from 0.1 to 80% by mass, more preferably from 0.2 to 70% by mass, Mass%. When the blending amount of the cellulose nanofibers having a carboxylate salt in the structure is 0.1% by mass or more, the desired effect of the present invention can be satisfactorily obtained. On the other hand, when the content is 80 mass% or less, film formability is improved.

The printed wiring board material of the present invention preferably comprises cellulose nanofibers (hereinafter also referred to as lignino cellulose nanofibers) having a number average fiber diameter of 3 nm to 1000 nm prepared from lignocellulose. Thus, such a cellulose nanofiber can be obtained as follows. It is possible to obtain a printed wiring board material capable of maintaining a high dielectric strength between circuits and maintaining high insulation reliability over a long period of time in a circuit of high precision and a large current application.

(Lignocellulose nanofiber)

The lignocellulose present in the natural world has a three-dimensional network hierarchical structure in which cellulose is firmly bonded to lignin and hemicellulose, and cellulosic molecules in the cell wall are not monomolecular but are aggregated regularly to form microfibrils Cellulosic nanofibers). 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, and bacterial cellulose produced by microorganisms. In order to produce the cellulose nanofibers from lignocellulose, a method in which the media is co-present and mechanically pulverized can be used.

Examples of the mechanical pulverizing method include a ball mill (vibrating ball mill, rotary ball mill, planetary ball mill), a rod mill, a bead mill, a disc mill, a cutter mill, a hammer mill, an impeller mill, an extruder, a mixer High-speed rotary blade type mixer, homomixer), homogenizer (high-pressure homogenizer, mechanical homogenizer, ultrasonic homogenizer). Among them, pulverization is preferably performed by a ball mill, a rod mill, a bead mill, a disc mill, a cutter mill, an extruder or a mixer. By using such a grinding method, cellulose nanofibers can be produced relatively easily. Further, the variation of the size of the obtained cellulose nanofibers becomes small.

The medium used in the pulverizing step is not particularly limited, but water, a low-molecular compound, a polymer compound, a fatty acid, and the like are suitably used. These may be used singly or in a mixture of two or more. Among them, it is preferable to use water as a milling medium by mixing a low molecular compound, a high molecular compound or a fatty acid with water.

Examples of the medium or low molecular weight compound include alcohols, ethers, ketones, sulfoxides, amides, amines, aromatics, morpholines and ionic liquids. Examples of the polymer compound include alcohol-based polymers, ether-based polymers, amide-based polymers, amine-based polymers, and aromatic-based polymers. Examples of the fatty acids include saturated fatty acids and unsaturated fatty acids. In this case, water-soluble low-molecular compounds, high-molecular compounds and fatty acids are preferably used.

In addition, prior to the pulverizing step, ozone treatment or the like may be performed as a pretreatment in order to facilitate pulverization.

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

In this case, the amount of the lignocellulosic nanofibers in the printed wiring board material is preferably from 0.1 to 80 mass%, more preferably from 0.2 to 70 mass%, more preferably from 0.2 to 70 mass%, based on the total amount of the composition, %to be. When the blending amount of the cellulose nanofibers is 0.1 mass% or more, the desired effect of the present invention can be satisfactorily obtained. On the other hand, when the content is 80 mass% or less, film formability is improved.

Example

Hereinafter, the present invention will be described in more detail with reference to examples. The numbers in the following tables indicate all parts by mass.

[Synthesis Example 1]

(Varnish 1)

A 2-liter separable flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen inlet tube was charged with 900 g of diethylene glycol dimethyl ether as a solvent and t-butylperoxy 2-ethylhexanoate (Trade name: PERBUTYL O), and the mixture was heated to 90 占 폚. 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 Co., Ltd., trade name: Flacklex FM1) (4-t-butylcyclohexyl) peroxydicarbonate (manufactured by Nichiyu K.K., trade name: Perillo TCP) was added dropwise over 3 hours. This was further aged for 6 hours to obtain a carboxyl group-containing copolymer resin. This reaction was carried out in a nitrogen atmosphere.

Subsequently, 363.9 g of 3,4-epoxycyclohexylmethylacrylate (manufactured by Daicel Co., Ltd., product name: Cychroma A200), 3.6 g of dimethylbenzylamine as a ring-opening catalyst, 10 g of hydroquinone mono 1.80 g of methyl ether was added, and the mixture was heated to 100 占 폚 and stirred to carry out a ring-opening addition reaction of epoxy. After 16 hours, a solution containing 53.8% by mass (nonvolatile content) of a carboxyl group-containing resin having an acid value of solid content of 108.9 mgKOH / g and a mass average molecular weight of 25,000 was obtained.

[Synthesis Example 2]

(Varnish 2)

Diethylene glycol monoethyl ether acetate as a solvent and azobisisobutyronitrile as a catalyst were placed in a flask equipped with a thermometer, a stirrer, a dropping funnel and a reflux condenser and heated at 80 DEG C under a nitrogen atmosphere to obtain methacryl The monomer mixture of acid and methyl methacrylate in a molar ratio of 0.40: 0.60 was added dropwise over about 2 hours. This was stirred for an additional hour, and then the temperature was elevated up to 115 DEG C and deactivated to obtain a resin solution.

After the resin solution was cooled, tetrabutylammonium bromide was used as a catalyst, and butylglycidyl ether was added at a molar ratio of 0.40 at 95 to 105 ° C for 30 hours to an equivalent amount of the carboxyl group of the obtained resin Lt; / RTI >

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

[Synthesis Example 3]

(Varnish 3)

210 g of cresol novolac epoxy resin (Epiclon N-680, epoxy equivalent = 210, manufactured by DIC Corporation) and 96.4 g of carbitol acetate as a solvent were placed in a flask equipped with a thermometer, a stirrer, a dropping funnel and a reflux condenser And dissolved by heating. To this, 0.1 g of hydroquinone as a polymerization inhibitor and 2.0 g of triphenylphosphine as a reaction catalyst were added. The mixture was heated to 95 to 105 DEG C, and 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 캜, 76.1 g of tetrahydrophthalic anhydride was added and reacted for about 6 hours by infrared absorption analysis until the absorption peak (1780 cm ^-1 ) of the acid anhydride disappeared. To this reaction solution, 96.4 g of aromatic solvent Solp # 150 manufactured by Idemitsu Kosan Co., Ltd. was added, diluted, and then removed. The carboxyl group-containing photosensitive polymer solution thus obtained had a nonvolatile content of 65% by mass and an acid value of a solid content of 78 mgKOH / g.

[Preparation of Cellulose Nanofiber Dispersion]

Cellulose nanofibers (BiNFi-s (bin piece), 10 mass% cellulose, number average fiber diameter 80 nm manufactured by Sugino Machine Co., Ltd.) were dehydrated and filtered, and 10 times the weight of the filtrate was added with carbitol acetate to obtain 30 After stirring for a few minutes, the mixture was filtered. This substitution operation was repeated three times, and carbitol acetate was added in an amount of 10 times the weight of the filtrate to prepare a cellulose nano fiber dispersion of 10 mass%.

≪ Example 1 >

* 1-1) Thermosetting compound 1: Epikote 828 manufactured by Mitsubishi Chemical Corporation

* 1-2) Thermosetting compound 2: Epikote 807 manufactured by Mitsubishi Chemical Corporation

* 1-3) Curing catalyst 1: 2MZ-A manufactured by Shikoku Kasei Kogyo Co., Ltd.

* 1-4) Acrylic copolymer compound 1: BYK-361N manufactured by Big Chem Japan Co., Ltd.

* 1-5) Acrylic copolymer compound 2: Polyflow No.50EHF (solid content 50% by mass) manufactured by KUMOMOTO KASEI CO., LTD.

* 1-6) Acrylic copolymer compound 3: Polyflow No. 90 manufactured by Sumoto Chemical Co., Ltd.

* 1-7) Colorant: phthalocyanine blue

* 1-8) Organic solvent: Carbitol acetate

* 1-9) Thermosetting compound 3: Unidick V-8000 (solid content 40% by mass) Manufactured by DIC Co., Ltd.

* 1-10) Thermosetting compound 4: Denacol EX-830 manufactured by Nagase Chemtex Co., Ltd.

* 1-11) Curing catalyst 2: Triphenylphosphine

* 1-12) Photocurable compound 1: Bisphenol A type epoxy acrylate Manufactured by Mitsubishi Chemical Corporation

* 1-13) Photocurable compound 2: Trimethylolpropane triacrylate

* 1-14) Photocurable compound 3: Kayama PM2 manufactured by Nippon Kayaku Co., Ltd.

* 1-15) Photocurable compound 4: Light ester HO Kyouta Shagaku Co., Ltd.

* 1-16) Photopolymerization initiator 1: 2-Ethylanthraquinone

* 1-17) Thermoplastic resin 1: Nova Tech PP BC03L manufactured by Nihon Polypro Co., Ltd.

* 1-18) Thermoplastic resin 2: Novatech LD LC561 manufactured by Nippon Polyethylene Co., Ltd.

* 1-19) Thermoplastic resin 3: Silicone SOXR-OB, varnish (solid content 70% by mass, N-methylpyrrolidone 30% by mass) manufactured by Nihon Kodoshi Kogyo Co.,

[Preparation of composition]

Examples 1-11 to 1-12 and Comparative Examples 1-1 to 1-3 in Table 1 and Table 2, Examples 1-19 to 1-21 in Table 4, and Comparative Examples 1-6, each component was compounded, stirred, and dispersed in a three-roll mill to prepare a composition, respectively.

[Production of composite molded article]

The components of Examples 1-13 to 1-15 and Comparative Example 1-4 in Table 3 were blended and then kneaded using a kneader (Labo Plastomill, manufactured by Toyo Seiki Co., Ltd.) to 180 Lt; 0 > C for 10 minutes at a revolution of 70 rpm. The obtained kneaded product was hot-pressed at 190 占 폚 and 0.5 MPa for 3 minutes and at 20 MPa for 1 minute using a pressing machine (Labo press P2-30T manufactured by Toyo Seiki Co., Ltd.) Lt; / RTI > for 1 minute. Thus, a sheet-shaped cellulose nanofiber composite formed article having a thickness of 0.05 mm was obtained.

Each of the components of Examples 1-16 to 1-18 and Comparative Example 1-5 in Table 3 was blended and then kneaded using a kneader (Labo Plastomill, manufactured by Toyo Seiki Co., Ltd.) to 150 Lt; 0 > C for 10 minutes at a revolution of 70 rpm. The resulting kneaded product was hot-pressed at 160 占 폚 and 0.5 MPa for 3 minutes and at 20 MPa for 1 minute using a press machine (Labo press P2-30T, manufactured by Toyo Seiki Co., Ltd.) Lt; / RTI > for 1 minute. Thus, a sheet-shaped cellulose nanofiber composite formed article having a thickness of 0.05 mm was obtained.

(Preparation of Test Piece for Evaluation of Smear Removability)

Fig. 2 is an explanatory diagram showing a manufacturing method of a substrate for smear removal evaluation. (A) to (c-1) in the drawing are plan views, and (c-2) is a sectional view of (c-1). 2, the compositions of Examples 1-1 to 1-6 and Comparative Example 1-1 were formed in the same manner as in Example 1-1 except that the conductive layer 13a was provided on the insulating layer 13b in a size of 50 mm x 50 mm Printed on an entire surface of a test substrate 13 of FR-4 copper-clad laminate (with copper pad, copper thickness of 18 탆) having a thickness of 1.6 mm and screen printing method, and cured at 140 캜 for 30 minutes in a hot air circulating type drying furnace , And an insulating resin layer 14 were formed. Subsequently, holes (vias) 15 having a diameter of 100 탆 were formed on the conductor layer 13a with a carbon dioxide gas laser to prepare test pieces.

The compositions of Examples 1-7 to 1-9 and Comparative Examples 1-2 were printed on the entire surface by the screen printing method on the test substrate and dried in a hot air circulation type drying furnace at 100 DEG C for 30 minutes Thereafter, a test piece was prepared in the same manner as described above, except that the insulating resin layer was formed by curing at 170 DEG C for 60 minutes.

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

Cellulose nanofiber composite molded articles having thicknesses of 0.05 mm in Examples 1-13 to 1-18 and Comparative Examples 1-4 and 1-5 were subjected to heat treatment at 190 占 폚 and 20 MPa for 1 minute , And further an insulating resin layer was formed by cold pressing at 23 占 폚 and 0.5 MPa for 1 minute to prepare a test piece in the same manner as described above.

The compositions of Examples 1-19 to 1-21 and Comparative Examples 1-6 were printed on the entire surface of the test substrate by screen printing and dried in a hot air circulation type drying furnace at 120 ° C for 10 minutes Thereafter, a test piece was prepared in the same manner as described above, except that the insulating resin layer was formed by curing at 250 占 폚 for 30 minutes.

(Smear removability)

Each test piece was immersed in a mixed solution of a Seqypose® MLB conditioner 211 (manufactured by Rohm and Haas Co., Ltd., 200 ml / l) and Seqypose® Z (manufactured by Rohm and Haas Company, 100 ml / l) as a swelling solution at 80 ° C for 5 minutes, Subsequently, the mixture was immersed in a mixed solution of a sucrose positive MLB promoter 213A (manufactured by Rohm and Haas Company, 100 ml / l) and a sucrose positive MLB promoter 213B (manufactured by Rohm and Haas Company, 150 ml / Finally, the solution was immersed in a Neutralizer 216-2 (manufactured by Rohm and Haas Co., Ltd., 200 ml / l) at 50 占 폚 for 5 minutes as a neutralizing solution. Thereafter, the via-bottom (copper surface) was observed with a scanning electron microscope (SEM, JSM-6610LV manufactured by Nihon Denshi Co., Ltd., magnification: 3,500 times), and the presence or absence of smear on the via- Respectively. The evaluation criteria are as follows. The evaluation results are shown in Tables 5 and 6 below.

(evaluation)

○: No smear

×: with smear

(Preparation of test pieces for evaluation of heat resistance, acid resistance and pencil hardness)

An insulating resin layer was formed on a test substrate of FR-4 copper laminate (copper thickness 18 占 퐉) having a size of 50 mm 占 50 mm and a thickness of 1.6 mm to prepare test pieces. The insulating resin layer was formed under the same conditions as those of the base material of the test piece for the smear removing property evaluation.

(Heat resistance)

Using each of the above-mentioned test pieces, a rosin-based flux was applied and then flowed for 30 seconds in a solder tank set at 260 ° C in advance, washed with propylene glycol monomethyl ether acetate and dried, and then subjected to a peeling test using a cellophane adhesive tape, 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 Tables 5 and 6 below.

(evaluation)

○: No peeling at the coating film

X: Peeling occurred in the coating film

(Acid resistance)

Each test piece was immersed in an aqueous 10% by volume sulfuric acid solution at 25 DEG C for 60 minutes, washed with water and dried. Thereafter, a peeling test using a cellophane adhesive tape was carried out to confirm whether or not the coating film was peeled off. The evaluation criteria are the same as the above heat resistance. The evaluation results are shown in Tables 5 and 6 below.

(Pencil hardness)

Using each of the above-mentioned test pieces, a polished B to 9H pencil was pressed at an angle of about 45 ° so that the end of the core was flattened, and the hardness of the pencil, in which peeling of the coating film did not occur, was recorded. The results are shown in Tables 5 and 6 below.

(Preparation of test piece for electrical insulation evaluation)

A comb-shaped electrode pattern of an IPC standard B pattern was prepared by an etching method using a FR-4 copper clad laminate (copper thickness: 18 mu m) having a size of 100 mm x 150 mm and a thickness of 1.6 mm to obtain a test substrate. On this test substrate, an insulating resin layer was formed so as to cover the interdigital electrode portion, thereby producing each test piece. The insulating resin layer was formed under the same conditions as those of the base material of the test piece for the smear removing property evaluation.

(Electrical insulation)

Using each test piece, a bias of 500 V DC was applied between the interdigital electrodes to measure the insulation resistance value. When the value was 100 G? Or more, it was indicated as?, And when it was less than 100 G? The results are shown in Tables 5 and 6 below.

(Production of test piece for evaluation of peel strength of plating layer)

An insulating resin layer was formed on a test substrate of FR-4 copper-clad laminate (copper thickness 18 占 퐉) having a size of 50 mm 占 50 mm and a thickness of 1.6 mm. The insulating resin layer was formed under the same conditions as those of the base material of the test piece for the smear removing property evaluation. Subsequently, a plating layer was formed on the entire surface of the insulating resin layer by an electroless copper plating method followed by an electrolytic copper plating method, thereby preparing respective test pieces.

(Peeling strength test of plating layer (peel strength test))

A sheath having a width of 10 mm and a length of 100 mm was inserted into the plating layer of each test piece, the one end was peeled and held by a holding member, and the load was measured when peeling 35 mm in the vertical direction at a rate of 50 mm / minute at room temperature. And when it is less than 0.8 kN / m, it is indicated as x. The results are shown in Tables 5 and 6 below.

As described above in detail, according to the printed wiring board material of the present invention, smear on the surface of the upper surface of the metal foil such as copper is hard to occur and can be easily removed even if it occurs. It has also been confirmed that the printed wiring board material of the present invention has sufficient properties as a solder resist and an interlayer insulating material.

≪ Example 2 >

[Production of evaluation sheet]

Each component was compounded, stirred, and dispersed in a three-roll mill according to the description in Table 7 below to prepare each composition. The addition amount of the cellulose nanofibers and the layer silicate was 10 mass% with respect to the total amount of the composition excluding the solvent. Subsequently, this composition was printed on a copper foil having a thickness of 18 占 퐉 on the entire surface by a screen printing method and cured at 140 占 폚 for 30 minutes in a hot-air circulation type drying furnace. Thereafter, the copper foil was removed to prepare a sheet having a thickness of 50 탆.

[Evaluation of linear expansion coefficient]

The sheet thus prepared was cut into a length of 3 mm width x 30 mm. This was heated from room temperature to 200 占 폚 at a rate of 5 占 폚 / min under a nitrogen atmosphere in a tensile mode with a chuck 10 mm and a load of 30 mN by using a thermomechanical analysis (EXSTAR6000) made by SII TMA (Thermomechanical Analysis) The temperature was lowered from 200 DEG C to 20 DEG C at 5 DEG C / min. Thereafter, the coefficient of linear expansion was determined from the measured values at 30 ° C to 100 ° C when the temperature was raised from 20 ° C to 200 ° C at 5 ° C / min. The evaluation results are shown in Table 7.

* 2-1) Thermosetting compound 1: Epikote 828 manufactured by Mitsubishi Chemical Corporation

* 2-2) Thermosetting compound 2: Epikote 807 manufactured by Mitsubishi Chemical Corporation

* 2-3) Curing catalyst 1: 2MZ-A manufactured by Shikoku Kasei Kogyo Co., Ltd.

* 2-4) Colorant: phthalocyanine blue

* 2-5) Layered silicate: manufactured by Lucentite STN Corp. Chemical Co., Ltd.

* 2-6) Organic solvent: Carbitol acetate

Each component was compounded, stirred, and dispersed in a three-roll mill according to the description in Table 8 below to prepare each composition. The addition amount of the cellulose nanofibers and the layer silicate was 10 mass% with respect to the total amount of the composition excluding the solvent. Then, this composition was printed on a copper foil having a thickness of 18 mu m on the entire surface by a screen printing method and dried in a hot air circulation type drying furnace at 100 DEG C for 30 minutes and cured at 170 DEG C for 60 minutes . Thereafter, the copper foil was removed, and the coefficient of linear expansion of the obtained sheet having a thickness of 50 mu m was measured.

* 2-7) Thermosetting compound 3: Unidick V-8000 (solid content 40% by mass) Manufactured by DIC Co., Ltd.

* 2-8) Thermosetting compound 4: Denacol EX-830 manufactured by Nagase Chemtex Co., Ltd.

* 2-9) Curing catalyst 2: Triphenylphosphine

Each component was blended and melt-kneaded at 180 ° C for 10 minutes at a rotation speed of 70 rpm using a kneader (Labo Plastomill, manufactured by Toyo Seiki Co., Ltd.). The addition amount of the cellulose nanofibers and the layer silicate was 10 mass% with respect to the total amount of the composition excluding the solvent. The obtained kneaded product was hot-pressed at 190 占 폚 and 0.5 MPa for 3 minutes and at 20 MPa for 1 minute using a pressing machine (Labo press P2-30T manufactured by Toyo Seiki Co., Ltd.) Lt; / RTI > for 1 minute. Thus, the coefficient of linear expansion of the obtained sheet of 50 mu m in thickness was measured.

* 2-10) Thermoplastic resin 1: Nova Tech PP BC03L manufactured by Nihon Polypro Co., Ltd.

Each component was blended and melt-kneaded at 150 ° C for 10 minutes at a rotation speed of 70 rpm using a kneader (Labo Plastomill, manufactured by Toyo Seiki Co., Ltd.). The addition amount of the cellulose nanofibers and the layer silicate was 10 mass% with respect to the total amount of the composition excluding the solvent. The resulting kneaded product was hot-pressed at 160 占 폚 and 0.5 MPa for 3 minutes and at 20 MPa for 1 minute using a press machine (Labo press P2-30T, manufactured by Toyo Seiki Co., Ltd.) Lt; / RTI > for 1 minute. Thus, the coefficient of linear expansion of the obtained sheet of 50 mu m in thickness was measured.

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

Each component was blended and stirred according to the description in Table 11 below, and dispersed in a three-roll mill to prepare each composition. The addition amount of the cellulose nanofibers and the layer silicate was 10 mass% with respect to the total amount of the composition excluding the solvent. Then, this composition was printed on a copper foil having a thickness of 18 mu m on the entire surface by a screen printing method, dried in a hot air circulating type drying furnace at 120 DEG C for 10 minutes, and cured at 250 DEG C for 30 minutes . Thereafter, the copper foil was removed, and the coefficient of linear expansion of the obtained sheet having a thickness of 50 mu m was measured.

* 2-12) Thermoplastic resin 3: Silicone SOXR-OB Varnish (solid content: 70% by mass), manufactured by Nihon Kodoshi Kogyo Co.,

Each component was compounded, stirred, and dispersed in a three-roll mill according to the description in Table 12 below to prepare each composition. The addition amount of the cellulose nanofibers and the layer silicate was 10 mass% with respect to the total amount of the composition excluding the solvent. Then, this composition was printed on a copper foil having a thickness of 18 mu m on the entire surface by a screen printing method and cured by irradiating with a metal halide lamp a total light quantity of ² J / cm2 at a wavelength of 350 nm. Thereafter, the copper foil was removed, and the coefficient of linear expansion of the obtained sheet having a thickness of 50 mu m was measured.

* 2-13) Photocurable compound 1: Bisphenol A type epoxy acrylate Manufactured by Mitsubishi Chemical Corporation

* 2-14) Photocurable compound 2: Trimethylolpropane triacrylate

* 2-15) Photocurable compound 3: Kayama PM2 manufactured by Nippon Kayaku Co., Ltd.

* 2-16) Photo-curable compound 4: Light ester HO Kyoe Shagaku Co., Ltd.

* 2-17) Photopolymerization initiator 1: 2-Ethylanthraquinone

Each component was blended and stirred according to the description in Tables 13 to 15 below, and dispersed with a three-roll mill to prepare each composition. The addition amount of the cellulose nanofibers and the layer silicate was 10 mass% with respect to the total amount of the composition excluding the solvent. Then, this composition was printed on a copper foil having a thickness of 18 占 퐉 on the entire surface by a screen printing method and dried in a hot air circulation type drying oven at 80 占 폚 for 30 minutes. Subsequently, using a negative pattern capable of covering the edge portion of the test substrate, exposure was performed with an integrated light quantity of 700 mJ / cm ² by an exposure device for printed wiring board HMW-680GW (manufactured by OAK Co., Ltd.) Of sodium carbonate aqueous solution as a developing solution for 60 seconds in a developing device for a printed wiring board to remove the rims. And then thermally cured at 150 캜 for 60 minutes in a hot air circulation type drying furnace. Thereafter, the copper foil was removed, and the coefficient of linear expansion of the obtained sheet having a thickness of 50 mu m was measured.

* 2-18) Curing catalyst 3: fine pulverized melamine manufactured by Nissan Chemical Industries, Ltd.

* 2-19) Curing catalyst 4: Dicyandiamide

* 2-20) Photopolymerization initiator 2: Irgacure 907 manufactured by BASF

* 2-21) Photocurable compound 5: Dipentaerythritol tetraacrylate

* 2-22) Thermosetting compound 5: TEPIC-H manufactured by Nissan Chemical Industries, Ltd.

As described in detail above, it was confirmed that the coefficient of linear expansion of the insulating material obtained by using the cellulose nanofibers in combination with the layered silicate was remarkably reduced.

≪ Example 3 >

* 3-1) Thermosetting compound 1: Epikote 828 manufactured by Mitsubishi Chemical Corporation

* 3-2) Thermosetting compound 2: Epikote 807 manufactured by Mitsubishi Chemical Corporation

* 3-3) Curing catalyst 1: 2MZ-A manufactured by Shikoku Kasei Kogyo Co., Ltd.

* 3-4) Colorant: phthalocyanine blue

* 3-5) Silicone compound 1: BYK-313 (solid content 15% by mass) Manufactured by Big Chem Japan Co., Ltd.

* 3-6) Silicone compound 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: Megaface RS-75 (solid content 40% by mass) Manufactured by DIC Co.

* 3-9) Fluorine compound 2: Asahi Guard AG-E300D (solid content 30% by mass) Manufactured by Asahi Glass Co., Ltd.

* 3-10) Organic solvent: Carbitol acetate

* 3-11) Thermosetting compound 3: Unidick V-8000 (solid content 40% by mass) Manufactured by DIC Co., Ltd.

* 3-12) Thermosetting compound 4: Denacol EX-830 manufactured by Nagase Chemtex Co., Ltd.

* 3-13) Thermosetting compound 5: TEPIC-H manufactured by Nissan Chemical Industries, Ltd.

* 3-14) Thermoplastic resin 1: Nova Tech PPBC03L manufactured by Nihon Polypro Co., Ltd.

* 3-15) Thermoplastic resin 2: Novatec LDLC561 manufactured by Nippon Polyethylene Co., Ltd.

* 3-16) Thermoplastic resin 3: Silicone SOXR-OB (solid content: 70% by mass) Varnishes manufactured by Nihon Kodoshi Kogyo Co.,

* 3-17) Photocurable compound 1: Bisphenol A type epoxy acrylate Manufactured by Mitsubishi Chemical Corporation

* 3-18) Photocurable compound 2: Trimethylolpropane triacrylate

* 3-19) Photocurable compound 3: Kayama PM2 manufactured by Nippon Kayaku Co., Ltd.

* 3-20) Photocurable compound 4: Light ester HO Kyoe Shagaku Co., Ltd.

* 3-21) Photocurable compound 5: Dipentaerythritol tetraacrylate

* 3-22) Curing catalyst 2: Triphenylphosphine

* 3-23) Curing catalyst 3: fine pulverized melamine manufactured by Nissan Chemical Industries, Ltd.

* 3-24) Curing catalyst 4: Dicyandiamide

* 3-25) Photopolymerization initiator 1: 2-Ethylanthraquinone

* 3-26) Photopolymerization initiator 2: Irgacure 907 manufactured by BASF

According to the formulation in the above table (except for Examples 3-14, 3-15, 3-22, 3-23, 3-3 and 3-4) And the mixture was stirred and dispersed in a three-roll mill to prepare a composition. The numbers in the tables indicate the mass parts.

For each of Examples 3-14, 3-22, and 3-3, each component was blended and heated at 180 ° C for 10 minutes using a kneader (Labo Plastomill, manufactured by Toyo Seiki Co., Ltd.) And melt-kneaded at a revolution of 70 rpm. The obtained kneaded product was hot-pressed at 190 占 폚 and 0.5 MPa for 3 minutes and at 20 MPa for 1 minute using a pressing machine (Labo press P2-30T manufactured by Toyo Seiki Co., Ltd.) Lt; / RTI > for 1 minute. Thus, a sheet-shaped cellulose nanofiber composite formed article having a thickness of 0.5 mm and a thickness of 0.05 mm was obtained.

For each of Examples 3-15, 3-23, and 3-4, each component was blended and heated at 150 ° C for 10 minutes using a kneader (Labo Plastomill, manufactured by Toyo Seiki Co., Ltd.) And melt-kneaded at a revolution of 70 rpm. The resulting kneaded product was hot-pressed at 160 占 폚 and 0.5 MPa for 3 minutes and at 20 MPa for 1 minute using a press machine (Labo press P2-30T, manufactured by Toyo Seiki Co., Ltd.) Lt; / RTI > for 1 minute. Thus, a sheet-shaped cellulose nanofiber composite formed article having a thickness of 0.5 mm and a thickness of 0.05 mm was obtained.

[Evaluation as interlayer insulating material]

(Preparation of test piece)

Fig. 3 is an explanatory diagram showing a method of manufacturing a substrate for evaluation of an interlayer insulating material. (A) to (e-1) in the drawing are plan views, and (e-2) is a sectional view of (e-1). 3, the compositions of Examples 3-1 to 3-12 and Comparative Example 3-1 were formed in the same manner as in Example 3-1 except that the conductive layer 21a was provided on the insulating layer 21b in a size of 50 mm x 50 mm Printed on the entire surface by a screen printing method on a test substrate 21 of a 1.6 mm FR-4 copper-clad laminate (with a copper pad and a copper thickness of 18 탆), and cured in a hot air circulating type drying furnace at 140 캜 for 30 minutes Thereby forming an insulating resin layer 22. Subsequently, a hole (via) 23 having a diameter of 100 탆 was formed on the conductor layer 21a with a carbon dioxide gas laser. Thereafter, the smear was removed with an aqueous potassium permanganate solution, electroless copper plating, The plating layer 24 was formed on the entire surface. Further, a wiring pattern 26 was formed by an etching method to prepare a test piece. Reference numeral 25 in the figure denotes an etching resist pattern.

The compositions of Examples 3-13, 3-21 and 3-2 were printed on the entire surface of the test board by screen printing and dried in a hot air circulating type drying oven at 100 ° C for 30 minutes And then cured at 170 DEG C for 60 minutes. Subsequently, a wiring pattern was formed in the same manner as described above to prepare a test piece.

The cellulose nano fiber composite molded article having a thickness of 0.05 mm including the examples 3-14, 3-15, 3-22, 3-23, 3-3 and 3-4, Was hot-pressed on the test substrate at 190 占 폚 and 20 MPa for 1 minute, and further cooled and pressed at 23 占 폚 and 0.5 MPa for 1 minute. Subsequently, a wiring pattern was formed in the same manner as described above to prepare a test piece.

The compositions of Examples 3-16, 3-24, and 3-5 were printed on the entire surface of the test substrate by screen printing, dried in a hot-air circulation type drying furnace at 120 ° C for 10 minutes, And then cured at 250 DEG C for 30 minutes. Subsequently, a wiring pattern was formed in the same manner as described above to prepare a test piece.

The compositions of Examples 3-17, 3-25, and 3-6 were printed on the entire surface of the test substrate by screen printing, and a metal halide lamp was charged with a total of ² J / cm ² at a wavelength of 350 nm The light amount was irradiated and cured. Subsequently, a wiring pattern was formed in the same manner as described above to prepare a test piece.

The compositions of Examples 3-18 to 3-20, Examples 3-26 to 3-28, and Comparative Examples 3-7 to 3-9 were printed on the entire surface by screen printing, And dried in a circulating type drying oven at 80 DEG C for 30 minutes. Subsequently, using a negative pattern capable of covering the edge portion of the test substrate, the resist film was exposed with an integrated light quantity of 700 mJ / cm ² using an exposure device HMW-680GW (manufactured by OAK Co., Ltd.) for a printed circuit board, and 1% The aqueous solution was used as a developing solution and developed for 60 seconds by a developing device for a printed wiring board, and the rim portion was then thermally cured in a hot air circulation type drying furnace at 150 캜 for 60 minutes. Subsequently, a wiring pattern was formed in the same manner as described above to prepare a test piece.

(Insulation reliability evaluation)

A DC voltage of 50 V was applied to the electrodes of six test specimens, and the test was conducted under the atmosphere of 130 캜 and 85%. The insulation resistance was measured in the test tank and the time at which it became one hundredth of the insulation resistance value after 1 hour from the start of the test was recorded. The fact that the insulation resistance value did not decrease after 100 hours was finished there. The results are shown in the following table.

[Evaluation as core material]

(Production of Cellulose Nanofiber Sheet)

For the cellulose nanofibers, a 0.2 mass% aqueous suspension was prepared with distilled water and filtered through a glass filter to form a sheet having a size of 50 mm x 50 mm and a thickness of 40 m.

(Example 3-29)

50 parts by mass of Epikote 828 manufactured by Mitsubishi Chemical Corporation, 50 parts by mass of Epikote 807 manufactured by Mitsubishi Chemical Corporation, and 1 part by mass of an acrylic copolymerizable compound (BYK-361N manufactured by BICKEMI Japan Co., Ltd.) 3 parts by mass of 2MZ-A manufactured by Shikoku Chemical Industry Co., Ltd., 2 parts by mass of BYK-313 manufactured by Big Chem Japan Co., Ltd., and 100 parts by mass of methyl ethyl ketone were mixed and stirred Solution. Each cellulosic nanofibre sheet was impregnated with the solution, allowed to stand in an atmosphere at 50 캜 for 12 hours, taken out, and dried at 80 캜 for 5 hours to prepare a prepreg. Ten sheets of the prepregs were superimposed and a copper foil having a thickness of 18 mu m was superimposed on the front and back sides and cured for 3 hours under the conditions of a temperature of 160 DEG C and a pressure of 2 MPa by means of a vacuum press machine. Then, as shown in Figs. 4A to 4C, the laminate 21 including the insulating layer 21b having the conductor layer 21a formed on both sides thereof was drilled to a drilled diameter of 300 mu m The through holes 27 were formed to have a pitch of 5 mm. Thereafter, the smear was removed by an aqueous solution of potassium permanganate, an electroless copper plating treatment and a subsequent electrolytic copper plating treatment were carried out to form a through hole 28. Then, as shown in Figs. 5 (a) to 5 (c), the wiring pattern 26 was produced by an etching method to obtain a test piece.

(Example 3-30)

50 parts by mass of Epikote 828 manufactured by Mitsubishi Chemical Corporation, 50 parts by mass of Epikote 807 manufactured by Mitsubishi Chemical Corporation, and 1 part by mass of an acrylic copolymerizable compound (BYK-361N manufactured by BICKEMI Japan Co., Ltd.) , 3 parts by mass of 2MZ-A (manufactured by Shikoku Chemical Industry Co., Ltd.), 0.75 parts by mass of Megaface RS-75 manufactured by DIC Corporation, and 100 parts by mass of methyl ethyl ketone were mixed and stirred to prepare a resin solution A test piece was obtained in the same manner as in Example 3-29.

(Comparative Example 3-10)

50 parts by mass of Epikote 828 manufactured by Mitsubishi Chemical Corporation, 50 parts by mass of Epikote 807 manufactured by Mitsubishi Chemical Corporation, 3 parts by mass of 2MZ-A (manufactured by Shikoku Chemicals Corporation) A test piece was obtained in the same manner as in Example 3-29 except that 100 parts by mass of methyl ethyl ketone was mixed and stirred to prepare a resin solution.

(Example 3-31)

, 100 parts by mass of Unidick V-8000 manufactured by DIC Corporation, 23 parts by mass of Denacol EX-830 manufactured by Nagase ChemteX Co., Ltd., an acrylic copolymer compound (BYK-361N, manufactured by Big Chem Japan Co., Ltd.) , 1 part by mass of triphenylphosphine, 2 parts by mass of BYK-313 manufactured by Big Chem Co., Ltd., and 100 parts by mass of methyl ethyl ketone were mixed and stirred to prepare a resin solution , A test piece was obtained in the same manner as in Examples 3-29.

(Example 3-32)

, 100 parts by mass of Unidick V-8000 manufactured by DIC Corporation, 23 parts by mass of Denacol EX-830 manufactured by Nagase ChemteX Co., Ltd., an acrylic copolymer compound (BYK-361N, manufactured by Big Chem Japan Co., Ltd.) , 1 part by mass of triphenylphosphine, 0.75 part by mass of Megaface RS-75 manufactured by DIC Corporation, and 100 parts by mass of methyl ethyl ketone were mixed and stirred to prepare a resin solution , And a test piece was obtained in the same manner as in Example 3-29.

(Comparative Example 3-11)

100 parts by mass of Unidick V-8000 manufactured by DIC Corporation, 23 parts by mass of Denacol EX-830 manufactured by Nagase Chemtech Co., Ltd., 1 part by mass of triphenylphosphine, 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 the components were mixed and stirred to prepare a resin solution.

(Example 3-33)

100 parts by mass of INCIS SOXR-OB manufactured by Nihon Kodoshi Kogyo Co., Ltd., 1 part by mass of an acrylic copolymerization compound (BYK-361N, manufactured by Big Chem Japan Co., Ltd.), BYK- 313, and 70 parts by mass of methyl ethyl ketone were mixed and stirred to prepare a resin solution. A test piece was obtained in the same manner as in Example 3-29.

(Example 3-34)

100 parts by mass of INCIS SOXR-OB manufactured by Nihon Kodoshi Kogyo Co., Ltd., 1 part by mass of an acrylic copolymerization compound (BYK-361N, manufactured by Big Chem Japan Co., Ltd.), 0.5 parts by mass of Megaface RS- And 70 parts by mass of methyl ethyl ketone were mixed and stirred to prepare a resin solution, a test piece was obtained in the same manner as in Example 3-29.

(Comparative Example 3-12)

A test piece was prepared in the same manner as in Example 3-29, except that 100 parts by mass of INCIS SOXR-OB manufactured by Nihon Kodoshi Kogyo Co., Ltd. and 70 parts by mass of methyl ethyl ketone were mixed and stirred to prepare a resin solution .

(Example 3-35)

18 mu m of copper foil was laminated on the front and back of the cellulose nanofiber composite formed article on the sheet of 0.5 mm in thickness in Examples 3-14 and heated for 1 minute under the conditions of a temperature of 190 DEG C and a pressure of 0.5 MPa by means of a vacuum press. Then, as shown in Figs. 4A to 4C, the laminate 21 including the insulating layer 21b having the conductor layer 21a formed on both sides thereof was drilled to a drilled diameter of 300 mu m The through holes 27 were formed to have a pitch of 5 mm. Thereafter, the smear was removed by an aqueous solution of potassium permanganate, electroless copper plating treatment, and then electrolytic copper plating treatment were carried out to form a through hole 28. Then, as shown in Figs. 5 (a) to 5 (c), the wiring pattern 26 was produced by an etching method to obtain a test piece.

(Example 3-36)

A test piece was prepared in the same manner as in Example 3-35 except that a sheet having a thickness of 0.5 mm 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 a sheet having a thickness of 0.5 mm in Comparative Example 3-3 was used.

(Example 3-37)

A test piece was produced in the same manner as in Example 3-35 except that a sheet having a thickness of 0.5 mm in Example 3-15 was used.

(Example 3-38)

A test piece was prepared in the same manner as in Example 3-35 except that a sheet having a thickness of 0.5 mm of Example 3-23 was used.

(Comparative Example 3-14)

A test piece was prepared in the same manner as in Example 3-35 except that a sheet having a thickness of 0.5 mm in Comparative Example 3-4 was used.

(Insulation reliability evaluation)

A DC voltage of 50 V was applied to the electrodes of six test specimens, and the test was conducted under the atmosphere of 130 캜 and 85%. The insulation resistance was measured in the test tank, and the time at which it became one hundredth of the insulation resistance value after one hour from the start of the test was recorded. The fact that the insulation resistance value did not decrease after 100 hours was terminated there.

As described in detail above, it has been confirmed that the insulating reliability to which the cellulose nanofibers are added is remarkably improved by the existence of either or both of the silicon compound and the fluorine compound.

<Example 4>

[Preparation of Cellulose Fiber Dispersion]

The softwood kraft pulp (NBKP) was mechanically treated with a high-pressure homogenizer, and the resulting cellulose fibers having a number average fiber diameter of 3 占 퐉 were added to water and sufficiently stirred to prepare a water suspension having a cellulose fiber content of 10% by mass. This was dehydrated and filtered, and 10 times the weight of the filtrate was added with carbitol acetate, stirred for 30 minutes, and then filtered. This substitution operation was repeated three times, and carbitol acetate was added in an amount of 10 times the weight of the filtrate to prepare a 10 mass% cellulose fiber dispersion.

[evaluation]

Each component was compounded, stirred, and dispersed in a three-roll mill according to the description in Tables 24 and 25 below to prepare each composition. The resulting composition was printed on an entire surface of a FR-4 copper-clad laminate (copper thickness 18 占 퐉) having a size of 150 mm x 100 mm with a thickness of 1.6 mm by screen printing and cured in a hot air circulating type drying oven at 140 占 폚 for 30 minutes . The film thickness after curing was 50 占 퐉. Thereafter, the surface of the cured product was roughened with an aqueous solution of potassium permanganate, and electroless copper plating and subsequent electrolytic copper plating were performed on the entire surface to prepare an evaluation board. (Peel strength) when a sheath portion having a width of 10 mm and a length of 100 mm was put on the copper plated portion and the one end portion was peeled and held by the holding member and 35 mm was peeled in the vertical direction at a rate of 50 mm / Were measured.

* 4-1) Thermosetting compound 1: Epikote 828 manufactured by Mitsubishi Chemical Corporation

* 4-2) Thermosetting compound 2: Epikote 807 manufactured by Mitsubishi Chemical Corporation

* 4-3) Curing catalyst 1: 2MZ-A manufactured by Shikoku Kasei Kogyo Co., Ltd.

* 4-4) Colorant: phthalocyanine blue

* 4-5) Organic solvent: Carbitol acetate

Each component was compounded, stirred, and dispersed in a three-roll mill according to the description in Tables 26 and 27 below to prepare each composition. The obtained composition was printed on an entire surface by a screen printing method on an FR-4 copper laminate (copper thickness: 18 탆) having a size of 150 mm x 100 mm and a thickness of 1.6 mm and dried in a hot air circulating type drying oven at 100 캜 for 30 minutes And then cured at 170 DEG C for 60 minutes. The film thickness after curing was 50 占 퐉. Thereafter, the surface of the cured product was roughened with an aqueous solution of potassium permanganate, and electroless copper plating and subsequent electrolytic copper plating were performed on the entire surface to prepare an evaluation board. (Peel strength) when a sheath portion having a width of 10 mm and a length of 100 mm was put on the copper plated portion and the one end portion was peeled and held by the holding member and 35 mm was peeled in the vertical direction at a rate of 50 mm / Were measured.

* 4-6) Thermosetting compound 3: Unidick V-8000 (solid content 40% by mass) Manufactured by DIC Co.

* 4-7) Thermosetting compound 4: Denacol EX-830 manufactured by Nagase Chemtex Co., Ltd.

* 4-8) Curing catalyst 2: Triphenylphosphine

Each component was blended and melt-kneaded at 180 ° C for 10 minutes at a rotation speed of 70 rpm using a kneader (Labo Plastomill, manufactured by Toyo Seiki Co., Ltd.) according to the description in Tables 28 and 29 below. The obtained kneaded product was hot-pressed at 190 占 폚 and 0.5 MPa for 3 minutes and at 20 MPa for 1 minute using a pressing machine (Labo press P2-30T manufactured by Toyo Seiki Co., Ltd.) Lt; / RTI &gt; for 1 minute. As a result, a sheet having a thickness of 50 mu m was obtained. This sheet was hot-pressed at 190 占 폚 and 20 MPa for 1 minute by hot pressing to an FR-4 copper-clad laminate (copper thickness 18 占 퐉) having a size of 150 mm 占 100 mm and a thickness of 1.6 mm and further heat- MPa for 1 minute to prepare a test piece. Thereafter, the surface of the cured product was roughened with an aqueous solution of potassium permanganate, and electroless copper plating and subsequent electrolytic copper plating were performed on the entire surface to prepare an evaluation board. (Peel strength) when a sheath portion having a width of 10 mm and a length of 100 mm was put on the copper plated portion and the one end portion was peeled and held by the holding member and 35 mm was peeled in the vertical direction at a rate of 50 mm / Were measured.

* 4-9) Thermoplastic resin 1: Nova Tech PP BC03L manufactured by Nihon Polypro Co., Ltd.

Each component was blended and melt-kneaded at 150 ° C for 10 minutes at a rotation speed of 70 rpm using a kneader (Labo Plastomill, manufactured by Toyo Seiki Co., Ltd.) according to the description in Tables 30 and 31 below. The resulting kneaded product was hot-pressed at 160 占 폚 and 0.5 MPa for 3 minutes and at 20 MPa for 1 minute using a press machine (Labo press P2-30T, manufactured by Toyo Seiki Co., Ltd.) Lt; / RTI &gt; for 1 minute. As a result, a sheet having a thickness of 50 mu m was obtained. The sheet was hot-pressed at 190 占 폚 and 20 MPa for 1 minute by hot pressing to an FR-4 copper-clad laminate (copper thickness 18 占 퐉) having a size of 150 mm x 100 mm and a thickness of 1.6 mm and further heat- For 1 minute to prepare a test piece. Thereafter, the surface of the cured product was roughened with an aqueous solution of potassium permanganate, and electroless copper plating and subsequent electrolytic copper plating were performed on the entire surface to prepare an evaluation board. (Peel strength) when a sheath portion having a width of 10 mm and a length of 100 mm was put on the copper plated portion and the one end portion was peeled and held by the holding member and 35 mm was peeled in the vertical direction at a rate of 50 mm / Were measured.

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

Each component was blended, stirred, and dispersed with a three-roll mill according to the description in Tables 32 and 33 below to prepare each composition. The resulting composition was printed on an entire surface of a FR-4 copper-clad laminate (copper thickness 18 占 퐉) having a size of 150 mm x 100 mm with a thickness of 1.6 mm by screen printing and dried in a hot air circulating type drying furnace at 120 占 폚 for 10 minutes And then cured at 250 DEG C for 30 minutes. The film thickness after curing was 50 占 퐉. Thereafter, the surface of the cured product was roughened with an aqueous solution of potassium permanganate, and electroless copper plating and subsequent electrolytic copper plating were performed on the entire surface to prepare an evaluation board. (Peel strength) when a sheath portion having a width of 10 mm and a length of 100 mm was put on the copper plated portion and the one end portion was peeled and held by the holding member and 35 mm was peeled in the vertical direction at a rate of 50 mm / Were measured.

* 4-11) Thermoplastic resin 3: Silicone SOXR-OB Varnish (solid content: 70% by mass), manufactured by Nihon Kodoshi Kogyo Co.,

The components were mixed, stirred, and dispersed in a three-roll mill according to the description in Tables 34 and 35 below to prepare each composition. The obtained composition was printed on an entire surface of a FR-4 copper-clad laminate (copper thickness 18 占 퐉) having a size of 150 mm x 100 mm with a thickness of 1.6 mm by screen printing, and a total area of ² J / cm &lt; The light amount was irradiated and cured. The film thickness after curing was 50 占 퐉. Thereafter, the surface of the cured product was roughened with an aqueous solution of potassium permanganate, and electroless copper plating and subsequent electrolytic copper plating were performed on the entire surface to prepare an evaluation board. (Peel strength) when a sheath portion having a width of 10 mm and a length of 100 mm was put on the copper plated portion and the one end portion was peeled and held by the holding member and 35 mm was peeled in the vertical direction at a rate of 50 mm / Were measured.

* 4-12) Photocurable compound 1: Bisphenol A type epoxy acrylate Manufactured by Mitsubishi Chemical Corporation

* 4-13) Photocurable compound 2: Trimethylolpropane triacrylate

* 4-14) Photocurable compound 3: Kayama PM2 manufactured by Nippon Kayaku Co., Ltd.

* 4-15) Photocurable compound 4: Light ester HO Kyoe Shagaku Co., Ltd.

* 4-16) Photopolymerization initiator 1: 2-Ethylanthraquinone

Each component was compounded, stirred, and dispersed in a three-roll mill according to the description in Tables 36 to 41 below to prepare each composition. The obtained composition was printed on an entire surface of a FR-4 copper-clad laminate (copper thickness 18 占 퐉) having a size of 150 mm x 100 mm and a thickness of 1.6 mm by screen printing and dried at 80 占 폚 for 30 minutes in a hot air circulation type drying furnace. Subsequently, using a negative pattern capable of covering the edge portion of the test substrate, the resist film was exposed with an integrated light quantity of 700 mJ / cm ² using an exposure device HMW-680GW (manufactured by OAK Co., Ltd.) for a printed circuit board, and 1% The aqueous solution was used as a developing solution for 60 seconds in a developing device for a printed wiring board, and the rim portion was then thermally cured in a hot air circulation type drying furnace at 150 캜 for 60 minutes. The film thickness after curing was 50 占 퐉. Thereafter, the surface of the cured product was roughened with an aqueous solution of potassium permanganate, and electroless copper plating and subsequent electrolytic copper plating were performed on the entire surface to prepare an evaluation board. (Peel strength) when a sheath portion having a width of 10 mm and a length of 100 mm was put on the copper plated portion and the one end portion was peeled and held by the holding member and 35 mm was peeled in the vertical direction at a rate of 50 mm / Were measured.

* 4-17) Curing catalyst 3: fine pulverized melamine manufactured by Nissan Chemical Industries, Ltd.

* 4-18) Curing catalyst 4: Dicyandiamide

* 4-19) Photopolymerization initiator 2: Irgacure 907 manufactured by BASF

* 4-20) Photocurable compound 5: Dipentaerythritol tetraacrylate

* 4-21) Thermosetting compound 5: TEPIC-H manufactured by Nissan Chemical Industries, Ltd.

As described in detail above, the use of an insulating material containing cellulose nanofibers having a number-average fiber diameter of 3 nm or more and less than 1000 nm and a cellulose fiber having a number average fiber diameter of 1 mu m or more was remarkably improved in peel strength.

&Lt; Example 5 >

[Preparation of Cellulose Nanofiber Dispersion Having Carboxylate Salt]

(Production Example 1)

5 g of softwood bleached kraft pulp (manufactured by Oji Paper Co., Ltd., moisture content 50 mass%, Canadian Standard Freeness (CSF) 550 ml, largely numbered average fiber diameter exceeding 1000 nm), 2,2,6,6-tetramethyl Was added to 500 mL of an aqueous solution containing 79 mg (0.5 mmol) of piperidine-N-oxyl (TEMPO) and 515 mg (5 mmol) of sodium bromide and stirred until the pulp was uniformly dispersed. To this was added 18 ml of an aqueous sodium hypochlorite solution containing 5% of effective chlorine, and the pH was adjusted to 10 with a 0.5N aqueous hydrochloric acid solution to initiate the oxidation reaction. During the reaction, the pH in the system was lowered, but a 0.5N aqueous solution of sodium hydroxide was added to adjust the pH to 10. After 2 hours of reaction, the mixture was filtered through a glass filter, and the filtrate was sufficiently washed with water to obtain a reaction product.

Next, distilled water was added to the reaction product to prepare an aqueous dispersion having a pulp concentration of 2% by mass, and the mixture was stirred and dispersed with a rotary-type mixer for 5 minutes. Since the viscosity of the slurry remarkably increased with stirring, distilled water was added little by little to continue stirring and dispersion by a mixer until the solid content concentration became 0.2 mass%, thereby obtaining a transparent gelated aqueous solution. This was observed with a TEM to confirm that it was an aqueous dispersion of a cellulose nanofiber having a carboxylic acid salt having a number average fiber diameter of 10 nm. The amount of the carboxyl group of the aqueous dispersion was 1.25 mmol / g.

This was dehydrated and filtered, and 10 times by weight of the filtrate was added with carbitol acetate, stirred for 30 minutes, and then filtered. This substitution operation was repeated three times, and 10 times the weight of the filtrate was added with carbitol acetate to prepare cellulose nano fiber dispersion 1 having 10 mass% of carboxylic acid salt.

(Production Example 2)

Instead of 79 mg (0.5 mmol) of 2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO) was added 4-dimethylamino-2,2,6,6-tetramethylpiperidine- 4-dimethylamino-TEMPO) was used in place of 100 mg (0.5 mmol) of the carboxylic acid salt in Example 1, to prepare a cellulose nanofiber dispersion 2 having a carboxylic acid salt of 10 mass%. The amount of the carboxyl group in the aqueous dispersion was 1.30 mmol / g, and the number average fiber diameter of the cellulose nanofibers having a carboxylate 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- -Carboxy-TEMPO) was used instead of 101 mg (0.5 mmol) of the carboxylic acid salt, to prepare a cellulose nanofiber dispersion 3 having a carboxylic acid salt of 10 mass%. Further, the amount of carboxyl group in the aqueous dispersion was 1.16 mmol / g, and the number average fiber diameter of the cellulose nanofibers having a carboxylate was 10 nm.

[Preparation of Cellulose Nanofiber Dispersion]

(Production Example 4)

The plate coated with eucalyptus was pulverized using a cutter mill to prepare a wood powder having a square size of 0.2 mm. Subsequently, the wood powder was subjected to high-temperature and high-pressure treatment in an aqueous solution such as sodium sulfite or sodium hydroxide to remove lignin. 50 times of distilled water was added and stirred. Mechanical grinding using a disc mill was carried out 15 times. Distilled water was added so as to be 10 mass% and stirred to obtain a cellulose nanofiber having a number average fiber diameter of 80 nm. This was subjected to dehydration filtration, carbitol acetate 10 times the weight of the filtrate was added, stirred for 30 minutes, and then filtered. This substitution operation was repeated three times, and 10 times the weight of the filtrate was added with carbitol acetate to prepare a cellulose nano fiber dispersion 1 of 10 mass%.

* 5-1) Thermosetting compound 1: Epikote 828 manufactured by Mitsubishi Chemical Corporation

* 5-2) Thermosetting compound 2: Epikote 807 manufactured by Mitsubishi Chemical Corporation

* 5-3) Curing catalyst 1: 2MZ-A manufactured by Shikoku Kasei Kogyo Co., Ltd.

* 5-4) Colorant: phthalocyanine blue

* 5-5) Organic solvent: Carbitol acetate

* 5-6) Thermosetting compound 3: manufactured by Unidick V-8000 DIC (solid content: 40% by mass)

* 5-7) Thermosetting compound 4: Denacol EX-830 manufactured by Nagase Chemtex Co., Ltd.

* 5-8) Curing catalyst 2: Triphenylphosphine

* 5-9) Thermoplastic resin 1: Silicone SOXR-OB Varnish (solid content 70% by mass, N-methylpyrrolidone 30% by mass), manufactured by Nihon Kodoshi Kogyo Co.,

* 5-10) Photocurable compound 1: Bisphenol A type epoxy acrylate Manufactured by Mitsubishi Chemical Corporation

* 5-11) Photocurable compound 2: Trimethylolpropane triacrylate

* 5-12) Photocurable compound 3: Kayama PM2 manufactured by Nippon Kayaku Co., Ltd.

* 5-13) Photocurable compound 4: Light ester HO Kyoe Shagaku Co., Ltd.

* 5-14) Photopolymerization initiator 1: 2-Ethylanthraquinone

* 5-15) Curing catalyst 3: fine pulverized melamine manufactured by Nissan Chemical Industries, Ltd.

* 5-16) Curing catalyst 4: Dicyandiamide

* 5-17) Photopolymerization initiator 2: Irgacure 907 BASF manufacture

* 5-18) Photocurable compound 5: Dipentaerythritol tetraacrylate

* 5-19) Thermosetting compound 5: TEPIC-H manufactured by Nissan Chemical Industries, Ltd.

[Preparation of sheet for evaluation of breaking strength and elongation at break]

Each component was compounded, stirred, and dispersed with a three-roll mill according to the description of Table 42 to prepare each composition. Subsequently, this composition was printed on a copper foil having a thickness of 18 占 퐉 on the entire surface by a screen printing method and cured at 140 占 폚 for 30 minutes in a hot-air circulation type drying furnace. Thereafter, the copper foil was removed to prepare an evaluation sheet having a thickness of 50 mu m.

Each component was compounded, stirred, and dispersed in a three-roll mill in accordance with the description in Table 43 to prepare each composition. Then, this composition was printed on a copper foil having a thickness of 18 mu m on the entire surface by a screen printing method and dried in a hot air circulation type drying furnace at 100 DEG C for 30 minutes and cured at 170 DEG C for 60 minutes . Thereafter, the copper foil was removed to prepare an evaluation sheet having a thickness of 50 mu m.

Each component was compounded, stirred, and dispersed in a three-roll mill in accordance with the description in Table 44 to prepare each composition. Then, this composition was printed on a copper foil having a thickness of 18 mu m on the entire surface by a screen printing method, dried in a hot air circulating type drying furnace at 120 DEG C for 10 minutes, and cured at 250 DEG C for 30 minutes . Thereafter, the copper foil was removed to prepare an evaluation sheet having a thickness of 50 mu m.

Each component was compounded, stirred, and dispersed in a three-roll mill in accordance with the description in Table 45 to prepare each composition. Then, this composition was printed on a copper foil having a thickness of 18 mu m on the entire surface by a screen printing method and cured by irradiating with a metal halide lamp a total light quantity of ² J / cm2 at a wavelength of 350 nm. Thereafter, the copper foil was removed to prepare an evaluation sheet having a thickness of 50 mu m.

According to the description of Tables 46 to 48, the respective components were compounded, stirred, and dispersed with a triaxial roll to prepare respective compositions. Then, this composition was printed on a copper foil having a thickness of 18 占 퐉 on the entire surface by screen printing and dried in a hot-air circulation type drying oven at 80 占 폚 for 30 minutes. Subsequently, using a negative pattern capable of covering the central portion of the copper foil, exposure was carried out with an integrated light quantity of 700 mJ / cm ² by an exposure machine HMW-680GW (manufactured by OAK Co., Ltd.) for printed wiring board, Of sodium carbonate aqueous solution as a developing solution for 60 seconds with a developing device for a printed wiring board to remove the copper foil edge portion. And then cured at 150 캜 for 60 minutes in a hot air circulation type drying furnace. Thereafter, the copper foil was removed to prepare an evaluation sheet having a thickness of 50 mu m.

[Evaluation of breaking strength and elongation at break]

According to JIS K7127, the above evaluation sheet was cut to a predetermined size to prepare a test piece. The test piece was measured for breaking strength [MPa] and elongation at break [%] at a tensile speed of 10 mm / min using a tensile tester (AGS-G manufactured by Shimadzu Corporation) Respectively. The results are shown in Tables 49 to 52 below. When both the breaking strength and the evaluation criteria of the elongation at break are &amp; cir &amp;, the cured product of the test piece has high toughness and excellent crack resistance.

(Evaluation Criteria of Breaking Strength)

○: 75 MPa or more

?: 50 MPa or more and less than 75 MPa

X: less than 50 MPa

(Evaluation Criteria of Elongation at Break)

○: 6% or more

?: 4% or more and less than 6%

×: less than 4%

[Preparation of substrate for evaluation of crack resistance]

The same procedure was followed except that a FR-4 copper clad laminate (copper thickness: 18 mu m) having a thickness of 1.6 mm was used in place of the copper foil in the production of the breaking strength and the elongation at break evaluation sheet, , An evaluation substrate having a cured product formed on the copper clad laminate was prepared.

[Evaluation of crack resistance]

The evaluation substrate was subjected to a temperature history of 1000 cycles with one cycle at -65 占 폚 for 30 minutes and 150 占 폚 for 30 minutes and the degree of cracking and peeling of the evaluation substrate thereafter was measured by an optical microscope ) Manufactured by Keyence VHX-2000) and evaluated based on the following evaluation criteria. The results are shown in Tables 49 to 52 below.

(Evaluation standard)

○: No crack occurred

C: Cracking occurred

X: Significant occurrence of cracks

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

&Lt; Example 6 >

[Production of lignocellulose nanofiber dispersion]

(Production Example 1)

The plate coated with eucalyptus was pulverized using a cutter mill to prepare a wood powder having a square size of 0.2 mm. Next, distilled water 50 times its mass was added to the wood powder, stirred, and subjected to mechanical pulverization 15 times using a disc mill. Distilled water was added thereto so as to be 10 mass% and stirred to obtain cellulose Nanofibers were obtained. This was dehydrated and filtered, and 10 times by weight of the filtrate was added with carbitol acetate, stirred for 30 minutes, and then filtered. This substitution operation was repeated three times, and carbitol acetate was added in an amount of 10 times the weight of the filtrate to prepare a lignocellulose nanofibre dispersion 1 of 10 mass%.

(Production Example 2)

The cedar-coated plate was milled using a cutter mill to produce wood flour about 0.2 mm square. Next, distilled water 50 times its mass was added to the wood powder, stirred, and subjected to mechanical pulverization 15 times using a disc mill. Distilled water was added thereto so as to be 10 mass% and stirred to obtain cellulose Nanofibers were obtained. This was dehydrated and filtered, and 10 times by weight of the filtrate was added with carbitol acetate, stirred for 30 minutes, and then filtered. This substitution operation was repeated three times, and carbitol acetate was added in an amount of 10 times the weight of the filtrate to prepare a lignocellulose nanofiber dispersion 2 of 10 mass%.

[Preparation of Dispersion of Cellulose Nanofibers for Comparison]

(Production Example 3)

The plate coated with eucalyptus was pulverized using a cutter mill to prepare a wood powder having a square size of 0.2 mm. Subsequently, the wood powder was subjected to high-temperature and high-pressure treatment in an aqueous solution such as sodium sulfite or sodium hydroxide to remove lignin. 50 times of distilled water was added thereto, and the mixture was stirred. Mechanical grinding using a disc mill was carried out 15 times. Distilled water was added so as to be 10 mass% and stirred to obtain a cellulose nanofiber with a number average fiber diameter of 80 nm. This was dehydrated and filtered, and 10 times by weight of the filtrate was added with carbitol acetate, stirred for 30 minutes, and then filtered. This substitution operation was repeated three times, and 10 times the weight of the filtrate was added with carbitol acetate to prepare a cellulose nano fiber dispersion 1 of 10 mass%.

[Production of printed wiring board material]

Each component was compounded, stirred, and dispersed with a three-roll mill according to the description in the following Tables 53, 54, and 57 to 61 to prepare each composition. The numbers in the following tables all represent the mass parts.

Each component was blended and melted and kneaded at 180 ° C for 10 minutes at a rotation speed of 70 rpm using a kneader (Labo Plastomill, manufactured by Toyo Seiki Co., Ltd.). The resultant kneaded product was hot-pressed at 190 占 폚 and 0.5 MPa for 3 minutes and at 20 MPa for 1 minute using a pressing machine (Labo press P2-30T manufactured by Toyo Seiki Co., Ltd.) Followed by cold pressing for 1 minute. Thus, sheet-shaped cellulose nanofiber composite molded articles each having a thickness of 0.5 mm and 0.05 mm were obtained, respectively.

Each component was blended and melt-kneaded at 150 ° C for 10 minutes at a rotation speed of 70 rpm using a kneader (Labo Plastomill, manufactured by Toyo Seiki Co., Ltd.). The resulting kneaded product was hot-pressed at 160 占 폚 and 0.5 MPa for 3 minutes and at 20 MPa for 1 minute using a pressing machine (Labo Press P2-30T manufactured by Toyo Seiki Co., Ltd.) Followed by cold pressing for 1 minute. Thus, sheet-shaped cellulose nanofiber composite molded articles each having a thickness of 0.5 mm and 0.05 mm were obtained, respectively.

* 6-1) Thermosetting compound 1: Epikote 828 manufactured by Mitsubishi Chemical Corporation

* 6-2) Thermosetting compound 2: Epikote 807 manufactured by Mitsubishi Chemical Corporation

* 6-3) Curing catalyst 1: 2MZ-A manufactured by Shikoku Kasei Kogyo Co., Ltd.

* 6-4) Pigment: phthalocyanine blue

* 6-5) Organic solvent: Carbitol acetate

* 6-6) Thermosetting compound 3: manufactured by Unidick V-8000 DIC (solid content: 40% by mass)

* 6-7) Thermosetting compound 4: Denacol EX-830 manufactured by Nagase Chemtex Co., Ltd.

* 6-8) Curing catalyst 2: Triphenylphosphine

* 6-9) Thermoplastic resin 1: Nova Tech PP BC03L manufactured by Nihon Polypro Co., Ltd.

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

* 6-11) Thermoplastic resin 3: Silicone SOXR-OB Varnish (solid content 70% by mass, N-methylpyrrolidone 30% by mass), manufactured by Nihon Kodoshi Kogyo Co.,

* 6-12) Photocurable compound 1: Bisphenol A type epoxy acrylate Manufactured by Mitsubishi Chemical Corporation

* 6-13) Photocurable compound 2: Trimethylolpropane triacrylate

* 6-14) Photocurable compound 3: Kayama PM2 manufactured by Nippon Kayaku Co., Ltd.

* 6-15) Photocurable compound 4: Light ester HO Kyoe Shagaku Co., Ltd.

* 6-16) Photopolymerization initiator 1: 2-Ethylanthraquinone

* 6-17) Curing catalyst 3: finely ground melamine (manufactured by Nissan Chemical Industries, 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 Industries, Ltd.)

[Evaluation as solder resist]

(Preparation of Test Substrate)

An interdigital electrode pattern of an IPC standard B pattern was produced by an etching method using an FR-4 copper clad laminate (copper thickness: 9 mu m) having a size of 100 mm x 150 mm and a thickness of 1.6 mm.

On the test substrate, the compositions of Examples 6-1 to 6-6 and Comparative Examples 6-1 and 6-2 were printed by a screen printing method so as to cover the interdigital electrodes, The test piece was cured under the condition of 30 minutes.

As a withstand voltage test, a DC voltage was applied to each of six test specimens at a boosting rate of 500 V / sec, and the voltage to be broken was measured. The results were evaluated as ○ when the average of 6 sheets was 4.5 kV or more, and by × when the average was less than 4.5 kV. The results are as follows: those of Examples 6-1 to 6-6 were all?, And those of Comparative Examples 6-1 and 6-2 were all?.

Further, as an insulation reliability test, a DC voltage of 50 V was applied to each of six test specimens, and the test was carried out under an atmosphere of 130 캜 and 85% RH to measure the time until a short circuit occurred. The evaluation was made when the average of six sheets was 200 hours or more, and when it was less than 200 hours. The results are as follows: those of Examples 6-1 to 6-6 were all?, And those of Comparative Examples 6-1 and 6-2 were all?.

On the test substrate, the compositions of Examples 6-7 to 6-12 and Comparative Examples 6-3 and 6-4 were printed by a screen printing method so as to cover the interdigital electrodes, and they were printed in a hot air circulation type drying furnace at 100 ° C, Dried for 30 minutes, and cured at 170 DEG C for 60 minutes to prepare a test piece.

As a withstand voltage test, a DC voltage was applied to each of six test specimens at a boosting rate of 500 V / sec, and the voltage to be broken was measured. The evaluation was made when the average of six sheets was 5.5 kV or more, and when it was less than 5.5 kV. The results were ○ for all of Examples 6-7 to 6-12, and X for Comparative Examples 6-3 and 6-4.

Further, as an insulation reliability test, a DC voltage of 50 V was applied to each of six test specimens, and the test was carried out under an atmosphere of 130 캜 and 85% RH to measure the time until a short circuit occurred. A case where the average of six sheets was 300 hours or more was evaluated as &amp; cir &amp; The results are as follows: those of Examples 6-7 to 6-12 were all?, And those of Comparative Examples 6-3 and 6-4 were?.

On the test substrate, a sheet having a thickness of 0.05 mm of each of Examples 6-13 to 6-24 and Comparative Examples 6-5 to 6-8 was cut out so as to cover the interdigital electrodes, , 20 MPa for 1 minute, and further cooled and pressed at 23 DEG 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 six test specimens at a boosting rate of 500 V / sec, and the voltage to be broken was measured. The results were evaluated as? When the average of six sheets was 3.5 kV or more, and by X when the average was less than 3.5 kV. The results are as follows: those of Examples 6-13 to 6-24 were all?, And those of Comparative Examples 6-5 to 6-8 were?.

Further, as an insulation reliability test, a DC voltage of 50 V was applied to each of six test specimens, and the test was carried out under an atmosphere of 130 캜 and 85% RH to measure the time until a short circuit occurred. The evaluation was made when the average of 6 sheets was 250 hours or more, and when it was less than 250 hours. The results are as follows: those of Examples 6-13 to 6-24 were all?, And those 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 printed on the test substrate by a screen printing method so as to cover the interdigital electrodes, Dried for 10 minutes, and cured at 250 DEG C for 30 minutes to prepare a test piece.

As a withstand voltage test, a DC voltage was applied to each of six test specimens at a boosting rate of 500 V / sec, and the voltage to be broken was measured. The evaluation was made when the average of six sheets was 5.5 kV or more, and when it was less than 5.5 kV. The results are as follows: those of Examples 6-25 to 6-30 were all?, And those of Comparative Examples 6-9 and 6-10 were?.

In addition, as the insulation reliability test, a DC voltage of 50 V was applied to each of six test specimens, and the test was conducted under an atmosphere of 130 캜 and 85% RH, and the time until the short circuit was measured. The evaluation was made when the average of 6 sheets was 250 hours or more, and when it was less than 250 hours. The results are as follows: those of Examples 6-25 to 6-30 were all?, And those of Comparative Examples 6-9 and 6-10 were?.

On the test substrate, the compositions of Examples 6-31 to 6-36 and Comparative Examples 6-11 and 6-12 were printed by a screen printing method so as to cover the interdigital electrodes. Subsequently, a metal halide lamp was irradiated with a wavelength of 350 nm Cm &lt; ² &gt; to obtain a test specimen.

As a withstand voltage test, a DC voltage was applied to each of six test specimens at a boosting rate of 500 V / sec, and the voltage to be broken was measured. The results were evaluated as? When the average of six sheets was 3.5 kV or more, and by X when the average was less than 3.5 kV. The results are as follows: those of Examples 6-31 to 6-36 were all?, And those of Comparative Examples 6-11 and 6-12 were?.

Further, as an insulation reliability test, a DC voltage of 50 V was applied to each of six test specimens, and the test was carried out under an atmosphere of 130 캜 and 85% RH to measure the time until a short circuit occurred. The evaluation was made when the average of six sheets was 100 hours or more, and when it was less than 100 hours. The results are as follows: those of Examples 6-31 to 6-36 were all?, And those of Comparative Examples 6-11 and 6-12 were?.

On the test substrate, the compositions of Examples 6-37 to 6-54 and Comparative Examples 6-13 to 6-18 were printed on the entire surface by a screen printing method using a 100 mesh polyester bias span , And dried in a hot air circulation type drying oven at 80 DEG C for 30 minutes. Subsequently, using a negative pattern that can be covered by the interdigital transducer, exposure was performed with an integrated light quantity of 700 mJ / cm ² using an exposure device HMW-680GW (manufactured by OAK Co., Ltd.) for a printed circuit board, and a 1% aqueous solution of sodium carbonate Was developed with a developing device for a printed wiring board for 60 seconds and then thermally cured at 150 캜 for 60 minutes in a hot air circulation type drying furnace to prepare a test piece.

As a withstand voltage test, a DC voltage was applied to each of six test specimens at a boosting rate of 500 V / sec, and the voltage to be broken was measured. The results were evaluated as ○ when the average of 6 sheets was 4.5 kV or more, and by × when the average was less than 4.5 kV. The results are the same as those of Examples 6-37 to 6-54, and those of Comparative Examples 6-13 to 6-18 were poor.

Further, as an insulation reliability test, a DC voltage of 50 V was applied to each of six test specimens, and the test was carried out under an atmosphere of 130 캜 and 85% RH to measure the time until a short circuit occurred. The evaluation was made when the average of six sheets was 200 hours or more, and when it was less than 200 hours. The results are the same as those of Examples 6-37 to 6-54, and those of Comparative Examples 6-13 to 6-18 were poor.

[Evaluation as interlayer insulating material]

The compositions of Examples 6-1 to 6-6 and Comparative Examples 6-1 and 6-2 were applied to FR-4 copper-clad laminate (copper thickness 9 μm) of 1.6 mm thickness with a size of 100 mm × 150 mm, Printed on the entire surface by a printing method, and cured in a hot air circulating type drying furnace at 140 DEG C for 30 minutes. Subsequently, electroless copper plating was performed, and then electrolytic copper plating was performed. Thereafter, a test piece having an interdigital electrode pattern of the IPC standard B pattern was produced by an etching method.

As a withstand voltage test, a DC voltage was applied to each of six test specimens at a boosting rate of 500 V / sec, and the voltage to be broken was measured. The evaluation was made when the average of six sheets was 5.5 kV or more, and when it was less than 5.5 kV. The results are as follows: those of Examples 6-1 to 6-6 were all?, And those of Comparative Examples 6-1 and 6-2 were all?.

Further, as an insulation reliability test, a DC voltage of 50 V was applied to each of six test specimens, and the test was carried out under an atmosphere of 130 캜 and 85% RH to measure the time until a short circuit occurred. The evaluation was made when the average of six sheets was 400 hours or more, and when it was less than 400 hours. The results are as follows: those of Examples 6-1 to 6-6 were all?, And those of Comparative Examples 6-1 and 6-2 were all?.

The compositions of Examples 6-7 to 6-12 and Comparative Examples 6-3 and 6-4 were laminated on a FR-4 copper-clad laminate (copper thickness 9 μm) of 1.6 mm thickness with a size of 100 mm × 150 mm, Printed on the entire surface by a printing method, dried in a hot air circulating type drying oven at 100 DEG C for 30 minutes, and cured at 170 DEG C for 60 minutes. Subsequently, electroless copper plating was performed, and then electrolytic copper plating was performed. Thereafter, a test piece having an interdigital electrode pattern of the IPC standard B pattern was produced by an etching method.

As a withstand voltage test, a DC voltage was applied to each of six test specimens at a boosting rate of 500 V / sec, and the voltage to be broken was measured. The results were evaluated as? When the average of six sheets was 6.5kV or more, and by X when the average was less than 6.5kV. The results are as follows: those of Examples 6-7 to 6-12 were all?, And those of Comparative Examples 6-3 and 6-4 were?.

Further, as an insulation reliability test, a DC voltage of 50 V was applied to each of six test specimens, and the test was carried out under an atmosphere of 130 캜 and 85% RH to measure the time until a short circuit occurred. The average of six sheets was rated as ◯ for 500 hours or more, and those for less than 500 hours as ×. The results were ○ for all of Examples 6-7 to 6-12, and those of Comparative Examples 6-3 and 6-4 were all negative.

Sheets having thicknesses of 0.05 mm in Examples 6-13 to 6-24 and Comparative Examples 6-5 to 6-8 were laminated on a FR-4 copper laminate having a thickness of 100 mm x 150 mm and a thickness of 1.6 mm 9 占 퐉) was hot-pressed at 190 占 폚 and 20 MPa for 1 minute by a hot press, and further cooled and pressed at 23 占 폚 and 0.5 MPa for 1 minute. Subsequently, electroless copper plating was performed, and then electrolytic copper plating was performed. Thereafter, a test piece having an interdigital electrode pattern of the IPC standard B pattern was produced by an etching method.

As a withstand voltage test, a DC voltage was applied to each of six test specimens at a boosting rate of 500 V / sec, and the voltage to be broken was measured. The results were evaluated as ○ when the average of 6 sheets was 4.5 kV or more, and by × when the average was less than 4.5 kV. The results are as follows: those of Examples 6-13 to 6-24 were all?, And those of Comparative Examples 6-5 to 6-8 were?.

Further, as an insulation reliability test, a DC voltage of 50 V was applied to each of six test specimens, and the test was carried out under an atmosphere of 130 캜 and 85% RH to measure the time until a short circuit occurred. The evaluation was made when the average of six sheets was 400 hours or more, and when it was less than 400 hours. The results are as follows: those of Examples 6-13 to 6-24 were all?, And those 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 laminated on a FR-4 copper laminate (copper thickness 9 μm) of 1.6 mm thickness with a size of 100 mm × 150 mm, Printed on the entire surface by a printing method, dried in a hot air circulating type drying furnace at 120 DEG C for 10 minutes, and cured at 250 DEG C for 30 minutes. Subsequently, electroless copper plating was performed, and then electrolytic copper plating was performed. Thereafter, a test piece having an interdigital electrode pattern of the IPC standard B pattern was produced by an etching method.

As a withstand voltage test, a DC voltage was applied to each of six test specimens at a boosting rate of 500 V / sec, and the voltage to be broken was measured. A case where the average of 6 sheets was 6 kV or more was evaluated as?, And a case of less than 6 kV was evaluated as?. The results are as follows: those of Examples 6-25 to 6-30 were all?, And those of Comparative Examples 6-9 and 6-10 were?.

Further, as an insulation reliability test, a DC voltage of 50 V was applied to each of six test specimens, and the test was carried out under an atmosphere of 130 캜 and 85% RH to measure the time until a short circuit occurred. The evaluation was made when the average of six sheets was 400 hours or more, and when it was less than 400 hours. The results are as follows: those of Examples 6-25 to 6-30 were all?, And those of Comparative Examples 6-9 and 6-10 were?.

The compositions of Examples 6-31 to 6-36 and Comparative Examples 6-11 and 6-12 were laminated on a FR-4 copper laminate (copper thickness 9 μm) of 1.6 mm thickness with a size of 100 mm × 150 mm, Printed on the entire surface by a printing method, and then cured by irradiating a total light quantity of ² J / cm ² with a wavelength of 350 nm with a metal halide lamp. Subsequently, electroless copper plating was performed, and then electrolytic copper plating was performed. Thereafter, a test piece having an interdigital electrode pattern of the IPC standard B pattern was produced by an etching method.

As a withstand voltage test, a DC voltage was applied to each of six test specimens at a boosting rate of 500 V / sec, and the voltage to be broken was measured. The results were evaluated as ○ when the average of 6 sheets was 4.5 kV or more, and by × when the average was less than 4.5 kV. The results are as follows: those of Examples 6-31 to 6-36 were all?, And those of Comparative Examples 6-11 and 6-12 were?.

Further, as an insulation reliability test, a DC voltage of 50 V was applied to each of six test specimens, and the test was carried out under an atmosphere of 130 캜 and 85% RH to measure the time until a short circuit occurred. The evaluation was made when the average of 6 sheets was 250 hours or more, and when it was less than 250 hours. The results are as follows: those of Examples 6-31 to 6-36 were all?, And those of Comparative Examples 6-11 and 6-12 were?.

The compositions of Examples 6-37 to 6-54 and Comparative Examples 6-13 to 6-18 were laminated on a FR-4 copper laminate (copper thickness 9 μm) having a size of 100 mm × 150 mm and a thickness of 1.6 mm , Was printed on the entire surface by a screen printing method using a 100 mesh polyester bias span and dried in a hot air circulation type drying oven at 80 DEG C for 30 minutes. Subsequently, the transparent PET film was exposed in an integrated light quantity of 700 mJ / cm ² using an exposure device HMW-680GW (manufactured by OAK Co., Ltd.) for a printed wiring board in place of the negative pattern, and a 1% aqueous solution of sodium carbonate , Developed for 60 seconds by a developing device for a printed wiring board, and subsequently subjected to thermal curing at 150 占 폚 for 60 minutes in a hot air circulation type drying furnace. Subsequently, electroless copper plating was performed, and then electrolytic copper plating was performed. Thereafter, a test piece having an interdigital electrode pattern of the IPC standard B pattern was produced by an etching method.

As a withstand voltage test, a DC voltage was applied to each of six test specimens at a boosting rate of 500 V / sec, and the voltage to be broken was measured. The evaluation was made when the average of six sheets was 5.5 kV or more, and when it was less than 5.5 kV. The results are the same as those of Examples 6-37 to 6-54, and those of Comparative Examples 6-13 to 6-18 were poor.

Further, as an insulation reliability test, a DC voltage of 50 V was applied to each of six test specimens, and the test was carried out under an atmosphere of 130 캜 and 85% RH to measure the time until a short circuit occurred. The evaluation was made when the average of six sheets was 400 hours or more, and when it was less than 400 hours. The results are the same as those of Examples 6-37 to 6-54, and those of Comparative Examples 6-13 to 6-18 were poor.

[Evaluation as core material]

(Preparation of lignocellulose nanofiber sheet)

A 0.2 mass% dispersion of carbinol acetate was prepared for the lignocellulose nanofiber dispersion 1 and the lignocellulose nanofiber dispersion 2, and the mixture was filtered with a glass filter to prepare a sheet having a size of 100 mm x 150 mm and a thickness of 40 m .

(Production of Cellulose Nanofiber Sheet)

A 0.2 mass% dispersion of carbitol acetate was prepared for the cellulose nanofiber dispersion 1 and filtered through a glass filter to prepare a sheet having a size of 100 mm x 150 mm and a thickness of 40 m.

50 parts by mass of Epikote 828 manufactured by Mitsubishi Chemical Corporation, 50 parts by mass of Epikote 807 manufactured by Mitsubishi Chemical Co., Ltd., 3 parts by mass of 2MZ-A manufactured by Shikoku Chemicals Corporation, 100 parts by mass of ethyl ketone was mixed and stirred to obtain a resin solution. Each cellulosic nanofibre sheet was impregnated with the solution, allowed to stand in an atmosphere at 50 캜 for 12 hours, taken out, and dried at 80 캜 for 5 hours to prepare a prepreg. 10 sheets of these prepregs were superimposed, and further copper foils having a thickness of 18 mu m were superimposed on the front and back surfaces and cured at a temperature of 160 DEG C and a pressure of 2 MPa for 3 hours by means of a vacuum press machine. Thereafter, a test piece having an interdigital electrode pattern of the IPC standard B pattern was produced by an etching method. The test piece of the lignocellulosic nanofiber dispersion 1 was changed to Example 6-55, the test piece of the lignocellulose nanofibre dispersion 2 was changed to the test piece of Example 6-56, the test piece of the cellulose nanofiber dispersion 1 was applied to the test piece of Comparative Example 6-19, And glass fibers were used in the same manner as in Comparative Example 6-20. The packing ratio of the cellulose fibers of Example 6-55, Examples 6-56, Comparative Examples 6-19 and 6-20 was 30% by mass. In Example 6-55 and Example 6-56, 1 part by mass of an acrylic copolymer compound (manufactured by BYK-361N Big Chem Co., Ltd.) was added.

As a withstand voltage test, a DC voltage was applied to each of six test specimens at a boosting rate of 500 V / sec, and the voltage to be broken was measured. The evaluation was made when the average of six sheets was 5.5 kV or more, and when it was less than 5.5 kV. The results are as follows: those of Examples 6-55 and 6-56 were all?, And those of Comparative Examples 6-19 and 6-20 were?.

Further, as an insulation reliability test, a DC voltage of 50 V was applied to each of six test specimens, and the test was carried out under an atmosphere of 130 캜 and 85% RH to measure the time until a short circuit occurred. The evaluation was made when the average of six sheets was 400 hours or more, and when it was less than 400 hours. The results are as follows: those of Examples 6-55 and 6-56 were all?, And those of Comparative Examples 6-19 and 6-20 were?.

100 parts by mass of Unidic V-8000 manufactured by DIC Corporation, 23 parts by mass of Denacol EX-830 manufactured by Nagase Chemtech Co., Ltd., 1 part by mass of triphenylphosphine, 100 parts by mass of methyl ethyl ketone And the mixture was stirred to obtain a resin solution. Each cellulosic nanofibre sheet was impregnated with the solution, allowed to stand in an atmosphere at 50 캜 for 12 hours, taken out, and dried at 80 캜 for 5 hours to prepare a prepreg. 10 sheets of the prepregs were superimposed and further 18 mu m of copper foil was superimposed on the front and back surfaces and cured for 3 hours under the conditions of a temperature of 160 DEG C and a pressure of 2 MPa with a vacuum press machine. Thereafter, a test piece having an interdigital electrode pattern of the IPC standard B pattern was produced by an etching method. The test piece of the lignocellulosic nanofiber dispersion 1 was changed to the test piece of Example 6-57, the test piece of the lignocellulose nanofibre dispersion 2 was changed to the test piece of Example 6-58, the test piece of the cellulose nanofibre dispersion 1 was replaced with the test piece of the cellulose nano- And glass fibers were used in the same manner as in Comparative Example 6-22. The packing ratio of the cellulose fibers of Examples 6-57, 6-58, 6-21 and 6-22 was 30% by mass. In Examples 6-57 and 6-58, 1 part by mass of an acrylic copolymer compound (manufactured by BYK-361N, Big Chem Co., Ltd.) was added.

As a withstand voltage test, a DC voltage was applied to each of six test specimens at a boosting rate of 500 V / sec, and the voltage to be broken was measured. The results were evaluated as? When the average of six sheets was 6.5kV or more, and by X when the average was less than 6.5kV. The results are as follows: those of Examples 6-57 and 6-58 were all?, And those of Comparative Examples 6-21 and 6-22 were?.

Further, as an insulation reliability test, a DC voltage of 50 V was applied to each of six test specimens, and the test was carried out under an atmosphere of 130 캜 and 85% RH to measure the time until a short circuit occurred. The evaluation was made when the average of 6 pieces was 500 hours or more, and when it was less than 500 hours, the evaluation was X. The results are as follows: those of Examples 6-57 and 6-58 were all?, And those of Comparative Examples 6-21 and 6-22 were?.

100 parts by mass of INCIS SOXR-OB manufactured by Nihon Kodoshi Kogyo Co., Ltd. and 70 parts by mass of methyl ethyl ketone were mixed and stirred to obtain a resin solution. Each cellulosic nanofibre sheet was impregnated with the solution, allowed to stand in an atmosphere at 50 캜 for 12 hours, taken out, and dried at 80 캜 for 5 hours to prepare a prepreg. 10 sheets of the prepregs were superimposed and further 18 mu m of copper foil was superimposed on the front and back surfaces and cured for 3 hours under the conditions of a temperature of 160 DEG C and a pressure of 2 MPa with a vacuum press machine. Thereafter, a test piece having an interdigital electrode pattern of the IPC standard B pattern was produced by an etching method. The test piece of the lignocellulosic nanofibre dispersion 1 was changed to the test piece of Example 6-59, the test piece of the lignocellulose nanofiber dispersion 2 was changed to the test piece of Example 6-60, the test piece of the cellulose nanofibre dispersion 1 was applied to the test piece of the comparative example 6-23 instead of the cellulose nano fiber And glass fibers were used in the same manner as in Comparative Example 6-24. The packing ratio of the cellulose fibers of Examples 6 to 59, Examples 6 to 60, Comparative Examples 6 to 23, and Comparative Examples 6 to 24 was 30 mass%. Further, in Examples 6-59 and 6-6, 1 part by mass of an acrylic copolymer compound (manufactured by BYK-361N Big Chem Co., Ltd.) was added.

As a withstand voltage test, a DC voltage was applied to each of six test specimens at a boosting rate of 500 V / sec, and the voltage to be broken was measured. A case where the average of 6 sheets was 6 kV or more was evaluated as?, And a case of less than 6 kV was evaluated as?. The results are as follows: those of Examples 6-59 and 6-60 were all?, And those of Comparative Examples 6-23 and 6-24 were?.

Further, as an insulation reliability test, a DC voltage of 50 V was applied to each of six test specimens, and the test was carried out under an atmosphere of 130 캜 and 85% RH to measure the time until a short circuit occurred. The evaluation was made when the average of six sheets was 400 hours or more, and when it was less than 400 hours. The results are as follows: those of Examples 6-59 and 6-60 were all?, And those of Comparative Examples 6-23 and 6-24 were?.

18 占 퐉 copper foils were stacked on the front and back sides of the sheets of 0.5 mm thickness in Examples 6-13 to 6-24 and Comparative Examples 6-5 to 6-8 and the temperature was 190 占 폚 and the pressure was 0.5 MPa Lt; 0 &gt; C for 1 minute. Thereafter, a test piece having an interdigital electrode pattern of the IPC standard B pattern was produced by an etching method.

As a withstand voltage test, a DC voltage was applied to each of six test specimens at a boosting rate of 500 V / sec, and the voltage to be broken was measured. The results were evaluated as ○ when the average of 6 sheets was 4.5 kV or more, and by × when the average was less than 4.5 kV. The results are as follows: those of Examples 6-13 to 6-24 were all?, And those of Comparative Examples 6-5 to 6-8 were?.

Further, as an insulation reliability test, a DC voltage of 50 V was applied to each of six test specimens, and the test was carried out under an atmosphere of 130 캜 and 85% RH to measure the time until a short circuit occurred. The evaluation was made when the average of six sheets was 400 hours or more, and when it was less than 400 hours. The results are as follows: those of Examples 6-13 to 6-24 were all?, And those of Comparative Examples 6-5 to 6-8 were?.

As described in detail above, it has been confirmed that by using the printed wiring board material containing the cellulose nanofibers prepared from lignocellulose, the withstand voltage and the insulation reliability, which have not been possible in the past, can be improved.

1, 3, 8, 11: conductor pattern
2: core substrate
1a and 4:
5: Through hole
6, 9: interlayer insulating layer
7, 10: Via
12: solder resist layer
13: copper-clad laminate (test board)
13a: conductor layer
13b: insulating layer
14: Insulating resin layer
15: laser vias
16: Plated layer
17: Etch resist pattern
18: wiring pattern
21: Copper clad laminate (test substrate)
21a: conductor layer
21b: insulating layer
22: Insulation resin layer
23: laser vias
24: Plating layer
25: etching resist pattern
26: wiring pattern
27: Through hole
28: Through hole

Claims (11)

A binder component, a cellulose nanofiber 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 a layered silicate. The printed wiring board material according to claim 1, comprising either or both of a silicon compound and a fluorine compound. The printed wiring board material according to claim 1, wherein the cellulose nanofibers further comprise a cellulose fiber having a number-average fiber diameter of 3 nm or more and less than 1000 nm and a number-average fiber diameter of 1 mu m or more. The printed wiring board material according to claim 1, wherein the cellulose nanofiber has a carboxylic acid salt in its structure. The printed wiring board material according to claim 1, wherein the cellulose nanofibers are produced from lignocellulose. The printed wiring board material according to claim 1, wherein the material is a solder resist. 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 characterized by using the printed wiring board material according to any one of claims 1 to 10.

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