KR102192598B1 - Printed-circuit-board material and printed circuit board using same - Google Patents

Abstract

The present invention provides a printed wiring board material that is less likely to cause smear on the upper surface of a metal foil such as copper and is easily removed even if it occurs, and a printed wiring board using the same. The printed wiring board material contains a binder component, cellulose nanofibers having a number average fiber diameter of 3 nm to 1000 nm, and an acrylic copolymer compound, and can be suitably used for solder resists and interlayer insulating materials for multilayer printed wiring boards. The printed wiring board uses this printed wiring board material.

Description

Printed wiring board material and printed wiring board using the same {PRINTED-CIRCUIT-BOARD MATERIAL AND PRINTED CIRCUIT BOARD USING SAME}

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

As a wiring board such as a printed wiring board, a metal foil such as copper is attached to a fiber such as a core material impregnated with an epoxy resin or the like, and a circuit is formed by an etching method, and further, an insulating resin composition is coated or sheet-shaped. After the insulating layer is formed by laminating the insulating resin composition, there is a circuit formed thereon. In addition, a solder resist is formed on the outermost layer of the wiring board for the purpose of protecting the formed circuit or mounting electronic components at correct positions. In general, an insulating material such as an epoxy resin or an acrylate resin is used for the solder resist (see, for example, Patent Documents 1, 2, and 3).

By the way, at the time of circuit formation, although a laser is used to form a hole (via) for interlayer conduction, there is a problem that smear (residue) is liable to remain on the upper surface (bottom of the via) of a metal foil such as copper. When attempting to strengthen the desmear treatment to remove smear at the bottom of the via, since the insulating layer is eroded, it becomes difficult to fill the via bottom and the inside of the via by plating (see, for example, Patent Document 4).

In addition, after removing a part of the solder resist to expose the circuit, component mounting is performed by soldering or the like, or wiring is taken out. When the circuit is exposed, a laser processing method in which a desired portion of the solder resist is removed by laser processing and the circuit is exposed is used, in addition to a photographic development method using a photosensitive solder resist which is a general method. However, in the laser processing method, there is a problem that smear (residue) is liable to remain similar to the formation of the interlayer conduction holes (vias) (see, for example, Patent Document 5).

Japanese Patent Application Publication No. 2006-182991 (Patent Claims, etc.) Japanese Patent Application Publication No. 2013-36042 (Patent Claims, etc.) Japanese Patent Laid-Open No. 08-269172 (Patent Claims, etc.) Japanese Patent Application Publication No. 2009-200301 (Patent Claims, etc.) Japanese Patent Laid-Open Publication No. 2010-031216 (Patent Claims, Paragraphs [0079] to [0086], etc.)

It is an object of the present invention to provide a printed wiring board material that is less likely to cause smear on the upper surface of a metal foil such as copper, and is easily removed even if it occurs, and a printed wiring board using the same.

As a result of intensive investigation, the present inventors have found that the above problems can be solved by using a material containing a cellulose nanofiber and an acrylic copolymer as a material for a printed wiring board, and the present invention has been completed.

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

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

It is preferable that the printed wiring board material of this invention contains a layered silicate. Moreover, it is preferable that the printed wiring board material of this invention contains either or both of a silicone compound and a fluorine compound. Moreover, in the printed wiring board material of this invention, it is preferable that the number average fiber diameter of the said cellulose nanofibers is 3 nm or more and less than 1000 nm, and it is preferable that the number average fiber diameter further contains cellulose fiber 1 micrometer or more.

In addition, in the printed wiring board material of the present invention, it is preferable that the cellulose nanofiber has a carboxylate in its structure. In addition, in the printed wiring board material of the present invention, it is preferable that the cellulose nanofibers are made of lignocellulose.

The printed wiring board material of the present invention can be suitably used for a solder resist and an interlayer insulating material of a multilayer printed wiring board.

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

According to the present invention, by using a material containing a cellulose nanofiber and an acrylic copolymer compound as a printed wiring board material, smear on the upper surface of a metal foil such as copper is hardly generated, and even if it occurs, a printed wiring board material and it It has become possible to realize the used printed wiring board.

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

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.

The printed wiring board material of the present invention is characterized in that it contains a binder component, cellulose nanofibers having a number average fiber diameter of 3 nm to 1000 nm, and an acrylic copolymer compound. The cellulose 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 cellulose nanofibers, pulp obtained from natural plant fiber raw materials such as wood, hemp, bamboo, cotton, jute, kenaf, beet, agricultural waste, cloth, and regenerated cellulose fibers such as rayon or cellophane can be used. Among them, pulp is particularly suitable. As the pulp, chemical pulp, such as kraft pulp and sulfurous acid pulp, obtained by pulping plant raw materials chemically or mechanically or in combination with both, semi-chemical pulp, semi-ground pulp, chemical mechanical pulp, thermomechanical pulp, chemical thermomechanical pulp , Refiner mechanical pulp, crushed wood pulp, and deinked waste paper pulp containing such plant fibers as a main component, magazine waste paper pulp, corrugated paper waste paper pulp, and the like may be used. Among them, various kinds of kraft pulp derived from conifers having strong fiber strength, such as unbleached softwood kraft pulp, unbleached softwood oxygen exposed kraft pulp, and softwood bleached kraft pulp are particularly suitable.

The raw material is mainly composed of cellulose, hemicellulose and lignin, of which the content of lignin is usually about 0 to 40% by mass, particularly about 0 to 10% by mass. For these raw materials, if necessary, lignin removal or bleaching treatment can be performed to adjust the amount of lignin. In addition, the measurement of the lignin content can be performed by the Klason method.

In the cell wall of plants, cellulose molecules are not single molecules but regularly aggregate to form dozens of crystalline microfibrils (cellulose nanofibers), which are the basic skeleton materials of plants. Therefore, in order to manufacture cellulose nanofibers from the raw materials, a method of unraveling the fibers to nano size by subjecting the raw materials to beating or pulverizing treatment, high-temperature high-pressure steam treatment, treatment with phosphate or the like can be used.

The beating or pulverizing treatment is a method of obtaining cellulose nanofibers by mechanically crushing or pulverizing by directly applying force to raw materials such as pulp to release fibers. More specifically, for example, pulp or the like is mechanically treated with a high-pressure homogenizer or the like, and the cellulose fibers unwound with a fiber diameter of about 0.1 to 10 µm are made into an aqueous suspension of about 0.1 to 3% by mass, and further By repeating the grinding or fusion treatment in the same manner as, cellulose nanofibers having a fiber diameter of about 10 to 100 nm can be obtained.

The said grinding or fusion treatment can be performed using, for example, a grinder "Pure Fine Mill" manufactured by Kurita Machinery Works. This grinder is a millstone type grinder that crushes raw materials into ultrafine particles by impact, centrifugal force, and shear force generated when raw materials pass through the gap between the upper and lower grinders. Shearing, grinding, atomizing, dispersing, emulsifying and fibril You can be angry at the same time. In addition, the said grinding or melting|fusing process can also be performed using the ultra-fine grinding machine "Super Mass Colloider" manufactured by Masyuki Industrial Co., Ltd. The Super Mass Colloider is a crusher that enables ultra-atomization that feels like melting beyond the realm of simple grinding. The super mass colloid is a millstone type ultra-fine grinder composed of two upper and lower non-granular grindstones that can freely adjust the interval. The upper grindstone is fixed and the lower grindstone rotates at high speed. The raw material put into the hopper is sent to the gap between the upper and lower grindstones by centrifugal force, and the raw material is gradually crushed and ultra-fine due to the strong compression, shear, and rolling frictional forces generated therein.

In addition, the high-temperature high-pressure steam treatment is a method of obtaining cellulose nanofibers by exposing raw materials such as pulp to high-temperature high-pressure steam to release fibers.

In addition, in the treatment with phosphate or the like, the surface of the raw material such as pulp is phosphate esterified to weaken the bonding strength between the cellulose fibers, and then, by performing a refiner treatment (grinding or fusion treatment) to release the fibers, cellulose This is a treatment method to obtain nanofibers. For example, the raw materials such as pulp are immersed in a solution containing 50% by mass of urea and 32% by mass of phosphoric acid, and the solution is sufficiently soaked between the cellulose fibers at 60°C, and then heated at 180°C to prevent phosphorylation. After proceeding and washing with water, hydrolysis treatment was performed at 60°C for 2 hours in a 3% by mass aqueous hydrochloric acid solution, followed by washing with water, and then further treatment at room temperature for about 20 minutes in a 3% by mass aqueous sodium carbonate solution. By doing so, phosphorylation is completed, and cellulose nanofibers can be obtained by dissolving this treated product with a refiner (such as the above-described crusher).

Further, the cellulose nanofibers used in the present invention may be chemically modified and/or physically modified to enhance functionality. Here, as the chemical modification, a functional group is added by acetalization, acetylation, cyanoethylation, etherification, isocyanate, etc., or an inorganic substance such as silicate or titanate is compounded or coated by a chemical reaction or a sol-gel method. It can be done by a method such as letting go. As a method of chemical modification, a method of heating by immersing cellulose nanofibers molded into a sheet in acetic anhydride is mentioned, for example. In addition, as a method of physical modification, for example, a metal or ceramic raw material can be used as a physical vapor deposition method (PVD method) such as vacuum vapor deposition, ion plating, sputtering, chemical vapor deposition method (CVD method), electroless plating or electrolytic plating. A method of coating by a plating method or the like is mentioned. These modifications may be performed before or after the 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, more preferably 3 nm to 100 nm. Since the minimum diameter of the short cellulose nanofibers is 3 nm, a material less than 3 nm cannot be produced substantially, and when it exceeds 1000 nm, dispersibility with the binder component deteriorates. In addition, the number average fiber diameter of the cellulose nanofibers is observed by SEM (Scanning Electron Microscope; scanning electron microscope) or TEM (Transmission Electron Microscope; transmission electron microscope), and draws a line diagonally in the photograph, and is in the vicinity thereof. It is a value obtained by measuring the remaining 10 points after randomly extracting 12 points of existing fibers, removing the thickest fibers and finest fibers.

The blending amount of the cellulose nanofibers used in the present invention is preferably 0.1 to 80% by mass, more preferably 0.2 to 70% by mass with respect to the total amount of the composition excluding the solvent. When the blending amount of the cellulose nanofibers is 0.1% by mass or more, the desired effect of the present invention can be obtained satisfactorily. On the other hand, when it is 80 mass% or less, film forming property improves.

Examples of the acrylic copolymer compound include poly(meth)acrylate, modified poly(meth)acrylate, and the like, and as specific examples thereof, BYK-350, BYK-352, BYK-354 manufactured by Big Chem Japan Co., Ltd. , BYK-355, BYK-356, BYK-358N, BYK-361N, BYK-380N, BYK-381, BYK-392, BYK-394, BYK-3440, BYK-3550, BYK-SILCLEAN3700, Disperbyk-2000, Disperbyk -2001, Disperbyk-2020, Disperbyk-2050, Disperbyk-2070, OX-880EF, OX-881, OX-883, OX-883HF, OX-77EF, OX-710, 1970, manufactured by Kusumoto Chemical Co., Ltd. 230, LF-1980, LF-1982, LF-1983, LF-1984, LF-1985, Polyflow No.7, Polyflow No.50E, Polyflow No.50EHF manufactured by Kyoesha Chemical Co., Ltd. Polyflow No.54N, Polyflow No.75, Polyflow No.77, Polyflow No.85, Polyflow No.85HF, Polyflow No.90, Polyflow No.90D-50, Polyflow No.95, Polyflow PW-95, Polyflow No.99C, etc. are mentioned, but are not limited to these. These may be used individually by 1 type, or may use 2 or more types together.

In addition, the blending amount of the acrylic copolymer compound used in the present invention is sufficient in a ratio commonly used, for example, preferably 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. If the blending amount of the acrylic copolymer compound is too small, there is a fear that the desired effect of the present invention may not be obtained, and if it is too large, a so-called bleed phenomenon occurs in which some liquid components of the acrylic copolymer compound in the cured product seep to the surface of the cured product. Therefore, either is not preferable.

(Binder component)

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

As a thermoplastic resin, acrylic, modified acrylic, low density polyethylene, high density polyethylene, ethylene-vinyl acetate copolymer, polyethylene terephthalate, polypropylene, modified polypropylene, polystyrene, acrylonitrile-butadiene-styrene copolymer, acrylonitrile-styrene General purpose plastics such as copolymer, cellulose acetate, polyvinyl alcohol, polyvinyl chloride, polyvinylidene chloride, and polylactic acid, polyamide, thermoplastic polyurethane, polyacetal, polycarbonate, ultra-high molecular weight polyethylene, polybutylene tere Phthalate, modified polyphenylene ether, polysulfone, polyphenylene sulfide, polyether sulfone, polyether ether ketone, polyallylate, polyetherimide, polyamideimide, liquid crystal polymer, polyamide 6T, polyamide 9T, polytetra Engineering plastics such as fluoroethylene, polyvinylidene fluoride, polyesterimide, and thermoplastic polyimide, thermoplastic elastomers such as olefins, styrenes, polyesters, urethanes, amides, vinyl chlorides, and hydrogenation systems. I can.

The thermosetting resin may be a resin that cures by heating and exhibits electrical insulating properties, 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 resin such as bisphenol P type epoxy resin, bisphenol Z type epoxy resin, bisphenol A novolac type epoxy resin, phenol novolak type epoxy resin, novolak type epoxy resin such as cresol novolac epoxy resin, biphenyl type epoxy Resin, biphenylaralkyl type epoxy resin, arylalkylene type epoxy resin, tetraphenylolethane 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 methacrylate copolymerized epoxy resin, cyclohexylmaleimide and glycidyl methacrylate copolymerized epoxy resin, 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 ether, tris(2,3-epoxypropyl)isocyanurate, triglycidyltris(2-hydroxyethyl)isocyanurate , Phenol novolac resin, cresol novolac resin, novolac-type phenol resin such as bisphenol A novolac resin, unmodified resorphenol resin, oil-modified resorphenol resin modified with tung oil, linseed oil, walnut oil, etc. Phenolic resins such as resor-type phenol resins, phenoxy resins, urea (urea) resins, triazine ring-containing resins such as melamine resins, unsaturated polyester resins, bismaleimide resins, diallylphthalate resins, silicone resins, benzoxazine rings Resin, norbornene resin, cyanate resin, isocyanate resin, urethane resin, benzocyclobutene resin, maleimide resin, bismaleimide triazine resin, polya Zomethine resin, thermosetting polyimide, etc. are mentioned.

As the radical polymerizable photocurable resin, any resin that exhibits electrical insulation by curing by irradiation with active energy rays may be used. In particular, a compound having at least one ethylenically unsaturated bond in the molecule is preferably used. As the compound having an ethylenically unsaturated bond, a well-known and common photopolymerizable oligomer, photopolymerizable vinyl monomer, and the like are used.

As a photopolymerizable oligomer, an unsaturated polyester type oligomer, a (meth)acrylate type oligomer, etc. are mentioned. Examples of (meth)acrylate oligomers include epoxy (meth)acrylates such as phenol novolac epoxy (meth)acrylate, cresol novolac epoxy (meth)acrylate, and bisphenol-type epoxy (meth)acrylate, and urethane (meth) Acrylate, epoxy urethane (meth)acrylate, polyester (meth)acrylate, polyether (meth)acrylate, polybutadiene-modified (meth)acrylate, and the like. In addition, in this specification, (meth)acrylate is a term which collectively refers to an acrylate, a methacrylate, and a mixture thereof, and the same applies to other similar expressions.

As a photopolymerizable vinyl monomer, it is a well-known thing, for example, styrene derivatives, such as styrene, chlorostyrene, and α-methylstyrene; Vinyl esters such as vinyl acetate, vinyl butyrate or vinyl benzoate; Vinyl isobutyl ether, vinyl-n-butyl ether, vinyl-t-butyl ether, vinyl-n-amyl ether, vinyl isoamyl ether, vinyl-n-octadecyl ether, vinyl cyclohexyl ether, ethylene glycol monobutyl vinyl Vinyl ethers such as ether and triethylene glycol monomethyl vinyl ether; Acrylamide, methacrylamide, N-hydroxymethylacrylamide, N-hydroxymethylmethacrylamide, N-methoxymethylacrylamide, N-ethoxymethylacrylamide, N-butoxymethylacrylamide, etc. Meth)acrylamides; Allyl compounds such as triallyl isocyanurate, diallyl phthalate, and diallyl isophthalate; 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isoboronyl (meth)acrylate, phenyl (meth)acrylate, phenoxyethyl (meth) ) 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; Ethylene glycol di(meth)acrylate, butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanedioldi(meth)acrylate, trimethylolpropane tri(meth)acrylate , Alkylene polyol poly(meth)acrylate such as pentaerythritol tetra(meth)acrylate and dipentaerythritol hexa(meth)acrylate; Polyoxyalkylene glycol poly(s) such as diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane tri(meth)acrylate, etc. Meth)acrylates; Poly(meth)acrylates such as hydroxypivalate neopentyl glycol ester di(meth)acrylate; Isocyanurate type poly(meth)acrylates, such as tris[(meth)acryloxyethyl]isocyanurate, etc. are mentioned.

As the cationic polymerizable photocurable resin, an alicyclic epoxy compound, an oxetane compound, a vinyl ether compound, and the like can be suitably used. Among these, as alicyclic epoxy compounds, 3,4,3',4'-diepoxybicyclohexyl, 2,2-bis(3,4-epoxycyclohexyl)propane, 2,2-bis(3,4-epoxy Cyclohexyl)-1,3-hexafluoropropane, bis(3,4-epoxycyclohexyl)methane, 1-[1,1-bis(3,4-epoxycyclohexyl)]ethylbenzene, bis(3, 4-epoxycyclohexyl) adipate, 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate, (3,4-epoxy-6-methylcyclohexyl) methyl-3',4' -Epoxy-6-methylcyclohexanecarboxylate, ethylene-1,2-bis (3,4-epoxycyclohexanecarboxylic acid) ester, cyclohexene oxide, 3,4-epoxycyclohexylmethyl alcohol, 3, And alicyclic epoxy compounds having an epoxy group such as 4-epoxycyclohexylethyltrimethoxysilane. As a commercial item, Daicel Co., Ltd. Celoxide 2000, Celoxide 2021, Celoxide 3000, EHPE3150; Epomic VG-3101 manufactured by Mitsui Chemical Co., Ltd.; E-1031S manufactured by Mitsubishi Chemical Corporation; TETRAD-X and TETRAD-C manufactured by Mitsubishi Gas Chemical Co., Ltd.; EPB-13, EPB-27 manufactured by Nippon Soda Co., Ltd. can be mentioned.

Examples of the oxetane compound include bis[(3-methyl-3-oxetanylmethoxy)methyl]ether, bis[(3-ethyl-3-oxetanylmethoxy)methyl]ether, and 1,4-bis[(3- Methyl-3-oxetanylmethoxy)methyl]benzene, 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, (3-methyl-3-oxetanyl)methylacrylate, (3-ethyl-3-oxetanyl)methylacrylate, (3-methyl-3-oxetanyl)methylmethacrylate, (3-ethyl-3-oxetanyl)methylmethacrylate or oligomers thereof Or, in addition to polyfunctional oxetanes such as copolymers, oxetane alcohol and novolac resin, poly(p-hydroxystyrene), cardo-type bisphenols, calixarenes, calixresorcinarenes, or silsesquioxane And oxetane compounds such as an etherified product of a resin having a hydroxyl group such as an oxetane ring and a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth)acrylate. As a commercial item, for example, Eternacol OXBP, OXMA, OXBP, EHO, xylylene bisoxetane manufactured by Ube Kosan Co., Ltd., Alon Oxetane OXT-101, OXT-201, OXT- manufactured by Toa Kose Co., Ltd. 211, OXT-221, OXT-212, OXT-610, PNOX-1009, etc. are mentioned.

Examples of the vinyl ether compound include cyclic ether-type vinyl ethers such as isosorbate divinyl ether and oxanorbornene divinyl ether (vinyl ethers having cyclic ether groups such as an oxirane ring, an oxetane ring, and an oxorane 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 hydroquinonedivinyl ether, 1,4-butanedioldivinyl ether, cyclohexanedivinyl ether, and cyclohexanedimethanoldivinyl ether, and having substituents such as alkyl groups and allyl groups at the α and/or β positions Vinyl ether compounds, etc. are mentioned. As a commercial product, for example, Maruzen Sekiyu Chemical Co., Ltd. 2-hydroxyethyl vinyl ether (HEVE), diethylene glycol monovinyl ether (DEGV), 2-hydroxybutyl vinyl ether (HBVE), tri Ethylene glycol divinyl ether, etc. are mentioned.

In addition, when using the printed wiring board material of the present invention as an alkali developing type photo solder resist capable of developing 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 photosensitive carboxyl group-containing resins having one or more photosensitive unsaturated double bonds, and carboxyl group-containing resins not having photosensitive unsaturated double bonds can be used, and are not limited to specific ones. As the carboxyl group-containing resin, in particular, resins listed below can be suitably used.

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

(2) A photosensitive carboxyl group-containing resin obtained by reacting a carboxyl group-containing (meth)acrylic copolymer resin with a compound having an oxirane ring and an ethylenically unsaturated group in one molecule.

(3) Reaction of an unsaturated monocarboxylic acid to a copolymer of a compound having an epoxy group and an unsaturated double bond and a compound having an unsaturated double bond in one molecule, and a secondary hydroxyl group produced by this reaction A photosensitive carboxyl group-containing resin obtained by reacting a saturated or unsaturated polybasic acid anhydride.

(4) A photosensitive hydroxyl group and carboxyl group obtained by reacting a hydroxyl-containing polymer with a saturated or unsaturated polybasic acid anhydride, and then reacting a compound having one epoxy group and an unsaturated double bond per molecule with the carboxylic acid produced by this reaction. Containing resin.

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

(6) A polyfunctional epoxy compound, a compound having two or more hydroxyl groups in one molecule, and one reactive group other than a hydroxyl group reacting with an epoxy group, and a monocarboxylic acid containing an unsaturated group were reacted, and a polybasic acid anhydride was added to the obtained reaction product. Carboxyl group-containing photosensitive resin obtained by making it react.

(7) 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 a polybasic acid anhydride with the obtained reaction product.

(8) A polyfunctional epoxy compound, a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group per molecule, and a monocarboxylic acid containing an unsaturated group are reacted, and a polybasic acid anhydride with respect to the alcoholic hydroxyl group of the obtained reaction product Carboxyl group-containing photosensitive resin obtained by reacting an anhydride group.

In the printed wiring board material of the present invention, in addition to the cellulose nanofibers, the binder component, and the acrylic copolymer compound, other commonly used blending components can be appropriately blended depending on the use.

As other common compounding components, a curing catalyst, a photoinitiator, a colorant, an organic solvent, etc. are mentioned, for example.

The curing catalyst is mainly for curing a thermosetting resin among curable resins, for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2- Imidazole derivatives such as phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, and 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole ; Amines such as dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, and 4-methyl-N,N-dimethylbenzylamine Hydrazine compounds such as compounds, adipic acid dihydrazide, and sebacic acid dihydrazide; And phosphorus compounds such as triphenylphosphine. In addition, as a commercial item, for example, 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (manufactured by Shikoku Kasei Kogyo Co., Ltd.), U-CAT3503N, U-CAT3502T, DBU, DBN, U-CATSA102, U- CAT5002 (manufactured by San-Apro Co., Ltd.) and the like, and may be used alone or in combination of two or more. Also similarly, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S- Triazine, 2-vinyl-4,6-diamino-S-triazine/isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine/isocyanure S-triazine derivatives such as acid adducts can also be used.

In addition, the photoinitiator is for curing the photocurable resin among the curable resins, for example, benzoin and benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether. ; 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-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone- Aminoalkylphenones such as 1, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone; Anthraquinones such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, and 1-chloroanthraquinone; Thioxanthones, such as 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, 2-chloro thioxanthone, and 2,4-diisopropyl thioxanthone; Ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; Benzophenones such as benzophenone; Or xanthones; (2,6-dimethoxybenzoyl)-2,4,4-pentylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide Phosphine oxides such as seeds and ethyl-2,4,6-trimethylbenzoylphenylphosphinate; Various peroxides, titanocene initiators, etc. are mentioned. These are photosensitizers such as tertiary amines such as N,N-dimethylaminobenzoic acid ethyl ester, N,N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylaminobenzoate, triethylamine, triethanolamine, etc. You may use it together. These photoinitiators can be used individually or in combination of 2 or more types.

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

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. 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 solvents, such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha, etc. are mentioned.

Further, if necessary, additives such as an antifoam/leveling agent, a thixotropy imparting agent/thickener, a coupling agent, a dispersant, and a flame retardant may be contained.

As the antifoaming agent and leveling agent, compounds such as silicone, modified silicone, mineral oil, vegetable oil, fatty alcohol, fatty acid, metal soap, fatty acid amide, polyoxyalkylene glycol, polyoxyalkylene alkyl ether, polyoxyalkylene fatty acid ester, etc. Can be used.

As a thixotropy-imparting agent and thickener, clay minerals such as kaolinite, smectite, montmorillonite, bentonite, talc, mica, zeolite, and fine particles silica, silica gel, irregular inorganic particles, polyamide additives, modified urea additives, wax additives, etc. You can use

As the coupling agent, the alkoxy group is a methoxy group, an ethoxy group, an acetyl, and the like, and as a reactive functional group, vinyl, methacrylic, acrylic, epoxy, cyclic epoxy, mercapto, amino, diamino, acid anhydride, ureido, sulfide, isocyanate Vinyl silane compounds such as vinyl ethoxy silane, vinyl trimethoxy silane, vinyl tris (β-methoxyethoxy) silane, γ-methacryloxypropyl trimethoxy silane, γ-aminopropyl Trimethoxysilane, N-β-(aminoethyl)γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)γ-aminopropylmethyldimethoxysilane, γ-ureidopropyltriethoxysilane, etc. Epoxy-based silane compounds such as amino-based silane compounds, γ-glycidoxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and γ-glycidoxypropylmethyldiethoxysilane, silane coupling agents such as mercapto-based silane compounds such as γ-mercaptopropyltrimethoxysilane, phenylamino-based silane compounds such as N-phenyl-γ-aminopropyltrimethoxysilane, and isopropyltriisostearoylated titanate , Tetraoctylbis(ditridecylphosphite) titanate, bis(dioctylpyrrophosphate)oxyacetate titanate, isopropyltridodecylbenzenesulfonyl titanate, isopropyltris(dioctylpyrophosphate) titanate , Tetraisopropylbis(dioctylphosphite)titanate, tetra(1,1-diallyloxymethyl-1-butyl)bis-(ditridecyl)phosphite titanate, bis(dioctylpyrophosphate)ethylene Titanate, isopropyltrioctanoyl titanate, isopropyldimethacryl isostearoyl titanate, isopropyltristearoyldiacryl titanate, isopropyltri(dioctylphosphate) titanate, isopropyltricumylphenyl Titanate-based coupling agents such as titanate, dicumylphenyloxyacetate titanate, diisostearoylethylene titanate, etc., ethylenically unsaturated zirconate-containing compounds, neoalkoxyzirconate-containing compounds, neoalkoxytris neodecanoyl Zirconate, neoalkoxytris(dodecyl)benzenesulfonylzirconate, neoalkoxytris(dioctyl)phosphate zirconate, neoalkoxytris(dioctyl)pyrophosphate zirconate, yes Oalkoxytris(ethylenediamino)ethylzirconate, neoalkoxytris(m-amino)phenylzirconate, tetra(2,2-diallyloxymethyl)butyl, di(ditridecyl)phosphytozirconate , Neopentyl(diallyl)oxy,trineodecanoylzirconate, neopentyl(diallyl)oxy,tri(dodecyl)benzene-sulfonylzirconate, neopentyl(diallyl)oxy, tri(dioctyl) ) Phosphatozirconate, neopentyl (diallyl) oxy, tri (dioctyl) pyro-phosphato zirconate, neopentyl (diallyl) oxy, tri (N-ethylenediamino) ethyl zirconate, neo Pentyl (diallyl) oxy, tri (m-amino) phenyl zirconate, neopentyl (diallyl) oxy, trimethacryl zirconate, neopentyl (diallyl) oxy, triacryl zirconate, dineopentyl (Diallyl)oxy,diparaaminobenzoylzirconate, dineopentyl(diallyl)oxy,di(3-mercapto)propionic zirconate, zirconium(IV)2,2-bis(2-propphenol) Zirconate-based coupling agents such as late methyl) butanolate, cyclodi[2,2-(bis2-propphenolatemethyl) butanolate] pyrophosphato-O,O, diisobutyl (oleyl) Aluminate-based coupling agents such as acetoacetyl aluminate and alkyl acetoacetate aluminum diisopropylate can be used.

Examples of the dispersant include polymeric dispersants such as polycarboxylic acid, naphthalene sulfonic acid formalin condensation system, polyethylene glycol, polycarboxylic acid partial alkyl ester system, polyether system, polyalkylene polyamine system, alkyl sulfonic acid system, quaternary ammonium system, Low molecular weight dispersants, such as higher alcohol alkylene oxide, polyhydric alcohol ester, and alkyl polyamine, can be used.

Examples of the flame retardant include hydrated metals such as aluminum hydroxide and magnesium hydroxide, red phosphorus, ammonium phosphate, ammonium carbonate, zinc borate, zinc stannate, molybdenum compound, bromine compound, chlorine compound, phosphate ester, phosphorus-containing polyol, phosphorus-containing amine, Melamine cyanurate, melamine compounds, triazine compounds, guanidine compounds, silicone polymers, and the like can be used.

Other compounding components include photoacid generators such as diazonium salts, sulfonium salts, and iodonium salts, photobase generators such as carbamate compounds, α-aminoketone compounds, and O-acyloxime compounds, barium sulfate, and spherical silica. , Inorganic fillers such as hydrotalcite, organic fillers such as silicon powder, nylon powder, and fluorine powder, radical scavengers, ultraviolet absorbers, peroxide decomposition agents, thermal polymerization inhibitors, adhesion promoters, and rust inhibitors.

The printed wiring board material according to the present invention having the configuration as described above can be suitably applied to a solder resist, and can also be suitably used for an interlayer insulating material of a multilayer printed wiring board, whereby in the obtained printed wiring board, The desired effect of the present invention can be obtained. In addition, when the present invention is applied to a printed wiring board material, for example, a method of forming a prepreg by molding the cellulose nanofibers into a sheet, impregnating and drying the sheet-like cellulose nanofibers with a binder component may also be used. I can.

1 is a partial cross-sectional view showing an example of a configuration of a multilayer printed wiring board according to the present invention. The illustrated multilayer printed wiring board can be manufactured as follows, for example. First, a through hole is formed in the core substrate 2 on which the conductor pattern 1 is formed. The through hole can be formed by suitable means such as a drill, a die punch, or a laser beam. After that, a roughening treatment is performed using a roughening agent. In general, the roughening treatment is swelled with an organic solvent such as N-methyl-2-pyrrolidone, N,N-dimethylformamide, or methoxypropanol, or an alkaline aqueous solution such as caustic soda or caustic potassium, and the like, and dichromate , Permanganate, ozone, hydrogen peroxide/sulfuric acid, nitric acid, and other oxidizing agents.

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

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

It is preferable that the printed wiring board material of this invention further contains a layered silicate. By combining and mixing the cellulose nanofibers and the layered silicate, it becomes possible to significantly reduce the linear expansion coefficient with a small amount of mixing compared to the case of mixing either one.

The layered silicate is not particularly limited, but clay minerals or hydrotalcite compounds having swellability and/or cleavage properties, and similar compounds thereof are preferable. Examples of these clay minerals include kaolinite, dicite, nacrite, haloysite, antigolite, chrysotile, pyrophyllite, montmorillonite, videlite, nontronite, saponite, sauconite, steben Site, hectorite, tetrasilica mica, sodium teniolite, muscovite mica, margarite, talc, vermiculite, gold mica, xandophilite, and chlorite. These layered silicates may be natural or synthetic. In addition, these layered silicates can be used alone 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 is not lipophilized is the thickness in one layer ( It is preferably about 1 nm). In addition, those having an average length of 0.01 to 50 µm, preferably 0.05 to 10 µm, and an aspect ratio of 20 to 500, preferably 50 to 200 may be suitably used.

The layered silicate has an inorganic cation capable of ion exchange between its layers. The ion-exchangeable inorganic cation refers to metal ions such as sodium, potassium, and lithium present on the crystal surface of the layered silicate. These ions have ion exchange properties with cationic substances, and various substances having cationic properties can be intercalated (intercalated) between the layers of the layered silicate by an ion exchange reaction.

The cation exchange capacity (CEC) of the layered silicate is not particularly limited, for example, it is preferably 25 to 200 meq/100g, more preferably 50 to 150 meq/100g, and still more preferably 90 to 130 meq/100g Do. When the cation exchange capacity of the layered silicate is 25 meq/100g or more, a sufficient amount of cationic material is intercalated (intercalated) between the layers of the layered silicate by ion exchange, so that the interlayers are sufficiently lipophilic. On the other hand, when the cation exchange capacity is 200 meq/100 g or less, the interlayer bonding strength of the layered silicate becomes too strong and the crystal flakes do not become difficult to peel, and good dispersibility can be maintained.

As a specific example of the layered silicate that satisfies the above suitable conditions, for example, Smekuton SA manufactured by Kunimine Kogyo Co., Ltd., Kunipia F manufactured by Kunimine Kogyo Corporation, and Somasif ME- manufactured by Cope Chemical Co., Ltd. Products such as 100 and Lucentite STN manufactured by Corp. Chemical Co., Ltd. are mentioned.

In addition, as the organic agent of the layered silicate used in the present invention, any general 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 Laid-Open Publication No. 2004-107541 It is preferable to use.

The method of containing the lipophilic agent between the layers of the layered silicate is not particularly limited, but from the viewpoint of easy synthesis operation, a method in which an inorganic cation is exchanged with a lipophilic agent by an ion exchange reaction to contain it is suitable. The method of ion-exchanging the ion-exchangeable inorganic cation of the layered silicate with the lipophilic agent is not particularly limited, and a known method can be used. Specifically, methods such as ion exchange in water, ion exchange in alcohol, and ion exchange in a water/alcohol mixed solvent can be used.

Specifically, after sufficiently solvating the layered silicate with water or alcohol, etc., a lipophilicating agent is added and stirred to replace the inorganic cations between the layers of the layered silicate with a lipophilicating agent. After that, the unsubstituted lipophilic agent is sufficiently washed, filtered out and dried. In addition, it is also possible to directly react the layered silicate and the organic cation in an organic solvent, or to react while heating and kneading the layered silicate and a lipophilic agent 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, a method of confirming the inorganic ions exchanged by the ICP emission spectrometry of the filtrate, a method of confirming that the layer spacing of the layered silicate has been extended by X-ray analysis, and the reduction of mass in the heating process by a thermal balance. It can be confirmed that the inorganic cation of the layered silicate has been substituted with the lipophilic agent by a method for confirming the presence of the lipophilic agent. The ion exchange is preferably 0.05 equivalent (5% by mass) or more, more preferably 0.1 equivalent (10% by mass) or more, and 0.5 equivalent (50% by mass) or more with respect to 1 equivalent of ion-exchangeable inorganic ions of the layered silicate. More preferable. The ion exchange is preferably performed at a temperature of 0 to 100°C, more preferably at a temperature of 10 to 90°C, and even more preferably at a temperature range of 15 to 80°C.

In addition, the blending amount of the layered silicate used in the present invention is preferably 0.02 to 48% by mass, more preferably 0.04 to 42% by mass with respect to the total amount of the composition excluding the solvent. When the blending amount of the layered silicate is 0.02% by mass or more, the effect of reducing the coefficient of linear expansion can be satisfactorily obtained. On the other hand, when it is 48 mass% or less, film forming property improves.

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

Moreover, it is preferable that the printed wiring board material of this invention contains either or both of a silicone 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 migration between holes.

(Silicone compound)

Examples of the silicone compound include polydimethylsiloxane, polyalkylphenylsiloxane, alkyl-modified silicone oil, polyether-modified silicone oil, polyalkylsiloxane, polymethylsilsesquioxane, polyalkylhydrogensiloxane, polyalkylalkenylsiloxane, and polymethylphenylsiloxane. , Aralkyl-modified silicone oil, alkylaralkyl-modified silicone oil, and the like. As a commercial item, BYK-300, BYK-302, BYK-306, BYK-307, BYK-310, BYK-313, BYK-330, BYK-331, BYK-333, BYK-337, BYK-341, BYK-344 , BYK-370, BYK375 (above, manufactured by Big Chem Japan Co., Ltd.), KS-66, KS-69, FZ-2110, FZ-2166, FZ-2154, FZ-2120, L-720, L-7002 , SH8700, L-7001, FZ-2123, SH8400, FZ-77, FZ-2164, FZ-2203, FZ-2208 (above, manufactured by Toray Dow Corning), KF-353, KF-615A, KF -640, KF-642, KF-643, KF-6020, X-22-6191, KF-6011, KF-6015, X-22-2516, KF-410, X-22-821, KF-412, KF -413, KF-4701 (above, manufactured by Shin-Etsu Chemical Co., Ltd.) is mentioned.

(Fluorine compound)

Examples of the fluorine compound include a fluorine-based resin having a perfluoroalkyl group or a perfluoroalkenyl group in the molecule. As a commercial item, for example, Megaface F-444, wing F-472, wing F-477, wing F-552, wing F-553, wing F-554, wing F-443, wing F-470, wing F- 470, wing F-475, wing F-482, wing F-483, wing F-489, wing R-30, wing RS-75 (above, manufactured by DIC Corporation), Ftop EF301, wing 303, wing 352 (Above, manufactured by Shin Akita Kasei Co., Ltd.), Florade FC-430, copper FC-431 (above, manufactured by Sumitomo 3M), Asahigard AG-E300D, Suflon S-382, Dong SC-101 , SC-102, SC-103, SC-104, SC-105, SC-106 (above, manufactured by Asahi Glass Co., Ltd.), BM-1000, BM-1100 (above, Yusho Co., Ltd.) ) Manufacturing), NBX-15, FTX-218 (above, manufactured by Neos Co., Ltd.) can be mentioned.

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

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

(Cellulose fiber)

The cellulose fiber can be obtained as follows.

As a raw material of the cellulose fiber, the thing similar to the said cellulose nanofiber is mentioned.

In order to produce a cellulose fiber from the raw material, a method of performing a beating or pulverizing treatment on the raw material can be used.

In the beating or pulverizing treatment, for example, pulp or the like is mechanically treated with a high-pressure homogenizer or the like, and the fiber diameter is released to about 1 to 10 µm, thereby obtaining a cellulose fiber as an aqueous suspension of about 0.1 to 3% by mass. .

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

Further, the cellulose fiber used in the present invention may be chemically modified and/or physically modified to enhance functionality, similar to the cellulose nanofibers.

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 described above.

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

In the present invention, in the manufacturing process of the cellulose nanofibers, when the fibers are released to the nano size, the treatment is stopped in the middle and the entire amount is not released, and the cellulose fibers in the range of the number average fiber diameter are also left behind. , A mixture of cellulose fibers and cellulose nanofibers satisfying the suitable 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 cellulose nanofibers satisfying the range of the specific number average fiber diameter, cellulose fibers having a number average fiber diameter outside the range of the specific number average fiber diameter are included. It may be.

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

According to the present invention, by combining and blending the cellulose fibers and the cellulose nanofibers, it is possible to achieve superior peel strength unprecedentedly. The mass ratio of the cellulose fiber and the cellulose nanofiber in the present invention is preferably 9:1 to 1:9, more preferably 8:2 to 2:8. Higher peel strength can be obtained by setting it within this range.

In this case, the total amount of the blending amount of the cellulose fiber and the cellulose nanofiber 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. Higher peel strength can be obtained by making the total amount of the blending amount of the cellulose fiber and the cellulose nanofibers 0.5% by mass or more, and good film-forming properties can be obtained by setting it as 80% by mass or less.

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

(Cellulose nanofibers having a carboxylate in the structure)

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

Next, in the aqueous dispersion, an N-oxyl compound is used as an oxidation catalyst, and the natural cellulose fiber is subjected to oxidation treatment. Examples of such N-oxyl compounds include TEMPO (2,2,6,6-tetramethylpiperidine-N-oxyl), 4-carboxy-TEMPO, 4-acetamide-TEMPO, and 4-amino-TEMPO. , 4-dimethylamino-TEMPO, 4-phosphonooxy-TEMPO, 4-hydroxyTEMPO, 4-oxyTEMPO, 4-methoxyTEMPO, 4-(2-bromoacetamide)-TEMPO, 2-azaa TEMPO derivatives having various functional groups at the C4 position, such as Damantan N-oxyl, may be used. As the addition amount of these N-oxyl compounds, a catalytic amount is sufficient, and it can usually be in a range of 0.1 to 10% by mass on an absolute dry basis with respect to natural cellulose fibers.

In the oxidation treatment of the natural cellulose fiber, an oxidizing agent and a co-oxidizing agent are used in combination. Examples of the oxidizing agent include, for example, ahalogenic acid, hypohalogenic acid and perhalogenic acid and their salts, hydrogen peroxide, and perorganic acids, and among them, alkali metal hypohalogen salts such as sodium hypochlorite and sodium hypobromite are used. Suitable. Further, as the co-oxidizing agent, an alkali metal bromide such as sodium bromide can be used, for example. The amount of oxidizing agent is usually in the range of about 1 to 100% by mass on an absolute dry basis with respect to natural cellulose fibers, and the amount of co-oxidizer is usually about 1 to 30% by mass on an absolute dry basis with respect to natural cellulose fibers. Range.

During the oxidation treatment of the natural cellulose fibers, 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. In addition, the temperature of the aqueous dispersion during the oxidation treatment can be arbitrarily set in the range of 1 to 50°C, and reaction is possible even at room temperature without temperature control. As reaction time, it can be set as the range of 1 to 240 minutes. In addition, a penetrating agent may be added to the aqueous dispersion in order to allow the drug to penetrate to the inside of the natural cellulose fiber and introduce more carboxyl groups to the fiber surface. Examples of the penetrating agent include anionic surfactants such as carboxylate, sulfate, sulfonate, and phosphate, and nonionic surfactants such as polyethylene glycol type and polyhydric alcohol type.

After the oxidation treatment of the natural cellulose fibers, prior to micronization, it is preferable to perform a purification treatment to remove impurities such as unreacted oxidizing agents and various by-products contained in the aqueous dispersion. Specifically, for example, a method of repeatedly washing and filtering the oxidized natural cellulose fibers with water can be used. The natural cellulose fibers obtained after the purification treatment are usually subjected to a micronization treatment in a state in which an appropriate amount of water is impregnated, but if necessary, a drying treatment may be performed to obtain a fibrous or powdery form.

Subsequently, the refinement of the natural cellulose treatment is carried out in a state in which the purified natural cellulose fibers are dispersed in a solvent such as water as desired. The solvent as the dispersion medium used in the micronization treatment is usually water, but if desired, alcohols (methanol, ethanol, isopropanol, isobutanol, sec-butanol, tert-butanol, methylcellosolve, ethylcello Solve, ethylene glycol, glycerin, etc.), ethers (ethylene glycol dimethyl ether, 1,4-dioxane, tetrahydrofuran, etc.), ketones (acetone, methyl ethyl ketone, N,N-dimethylformamide, N,N- An organic solvent soluble in water, such as dimethylacetamide, dimethyl sulfoxide, etc.) may be used, or a mixture thereof may be used. The solid content concentration of the natural cellulose fibers in the dispersion of these solvents is preferably 50% by mass or less. When the solid content concentration of the natural cellulose fiber exceeds 50% by mass, it is not preferable because very high energy is required for dispersion. The refinement of natural cellulose treatment is the dispersion of low pressure homogenizers, high pressure homogenizers, grinders, cutter mills, ball mills, jet mills, beating machines, mixers, single screw extruders, twin screw extruders, ultrasonic stirrers, home juicer mixers, etc. It can be done using a device.

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

By the oxidation treatment and micronization treatment of the natural cellulose fiber, 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 such a carboxyl group is 0.1 to 3 mmol/g. Thus, highly crystalline cellulose nanofibers having the predetermined number average fiber diameter can be obtained. This highly crystalline cellulose nanofiber has a cellulose I-type crystal structure. This means that these cellulose nanofibers are micronized by surface oxidation of naturally-derived cellulose molecules having an I-type crystal structure. In other words, in natural cellulose fibers, fine fibers called microfibrils produced in the process of their biosynthesis are multi-bundled to build a high-order solid structure, and strong cohesion between the microfibrils (hydrogen bonds between surfaces ) Is weakened by introduction of an aldehyde group or carboxyl group by oxidation treatment, and further subjected to a micronization treatment, whereby cellulose nanofibers are obtained. By adjusting the conditions of the oxidation treatment, the polarity can be changed by increasing or decreasing the content of the carboxyl group, or the average fiber diameter, average fiber length, and average aspect ratio of the cellulose nanofibers can be controlled by electrostatic repulsion or micronization treatment of the carboxyl group. have.

That the natural cellulose fiber has an I-type crystal structure shows typical peaks at two positions near 2θ = 14 to 17° and around 2θ = 22 to 23° in the diffraction profile obtained by measurement of its wide-angle X-ray diffraction image. Because we have, we can sympathize. In addition, the presence of a carboxyl group in the cellulose molecule of the cellulose nanofiber can be confirmed by the presence of absorption (near 1608 cm ^-1 ) due to a carbonyl group in the total reflection infrared spectral spectrum (ATR) in the sample from which moisture was completely removed. have. In the case of a carboxyl group (COOH), absorption exists at 1730 cm ^-1 in the above measurement.

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

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

In addition, the amount [mmol/g] of carboxyl groups in cellulose relative to the weight of the cellulose nanofibers contained in the aqueous dispersion can be evaluated by the following method. That is, 60 ml of an aqueous dispersion of 0.5 to 1% by mass of a cellulose nanofiber sample whose dry weight was accurately weighed in advance was prepared, the pH was set to about 2.5 with a 0.1 M aqueous hydrochloric acid solution, and the pH of 0.05 M aqueous sodium hydroxide solution was about It is dripped until 11, and 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 electrical conductivity is gentle, the amount of functional groups can be determined using the following equation. The amount of this functional group represents the amount of the carboxyl group.

Functional group [mmol/g]=V[ml]×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 similar to that of the cellulose nanofibers.

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

Further, the printed wiring board material of the present invention preferably contains cellulose nanofibers (hereinafter also referred to as lignocellulose nanofibers) having a number average fiber diameter of 3 nm to 1000 nm made from lignocellulose. Thereby, such cellulose nanofibers can be obtained as follows. In high-precision circuits and high-current applications, it is possible to obtain a printed wiring board material that has a high withstand voltage between circuits and can maintain high insulation reliability over a long period of time.

(Lignocellulose nanofiber)

Lignocellulose existing in nature has a three-dimensional network hierarchical structure in which cellulose is firmly linked to lignin and hemicellulose, so that cellulose molecules in the cell wall are not single molecules but regularly aggregated to collect dozens of microfibrils ( Cellulose nanofibers). Specifically, the lignocellulose used in the present invention can be obtained, for example, from woody biomass obtained from plants such as wood, agricultural products, vegetation, and cotton, and bacterial cellulose produced by microorganisms. In order to produce cellulose nanofibers from lignocellulose, a method of mechanically pulverizing by coexisting a medium can be used.

Examples of such mechanical grinding methods include ball mills (vibrating ball mills, rotary ball mills, planetary ball mills), rod mills, bead mills, disk mills, cutter mills, hammer mills, impeller mills, extruders, mixers ( A high-speed rotating blade type mixer, a homomixer), a homogenizer (high pressure homogenizer, mechanical homogenizer, ultrasonic homogenizer), and the like. Among these, pulverization is preferably performed by a ball mill, rod mill, bead mill, disk mill, cutter mill, extruder or mixer. By using such a pulverization method, cellulose nanofibers can be produced relatively easily. In addition, variations in the size of the resulting cellulose nanofibers are reduced.

The medium used in the pulverization step is not particularly limited, but water, low molecular weight compounds, high molecular weight compounds, fatty acids, and the like are suitably used. These may be used individually by 1 type, and may mix and use 2 or more types. Among these, it is preferable to mix water, a low molecular weight compound, a high molecular compound, or a fatty acid, and use it as a pulverizing medium.

Among the above, examples of the low molecular weight compound include alcohols, ethers, ketones, sulfoxides, amides, amines, aromatics, morpholines, and ionic liquids. Further, examples of the polymer compound include alcohol-based polymers, ether-based polymers, amide-based polymers, amine-based polymers, and aromatic polymers. Moreover, saturated fatty acids, unsaturated fatty acids, etc. are mentioned as fatty acids. In this case, it is preferable to use a water-soluble one as the low-molecular compound, high-molecular compound and fatty acid to be used.

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

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

In this case, the blending amount of the lignocellulosic nanofibers in the printed wiring board material is preferably 0.1 to 80% by mass, more preferably 0.2 to 70% by mass, based on the total amount of the composition excluding the organic solvent described later. %to be. When the blending amount of the cellulose nanofibers is 0.1% by mass or more, the desired effect of the present invention can be obtained satisfactorily. On the other hand, when it is 80 mass% or less, film forming property improves.

Example

Hereinafter, the present invention will be described in more detail using examples. In addition, all the numbers in the following table represent parts by mass.

[Synthesis Example 1]

(Varnish 1)

In a 2-liter separable flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel, and nitrogen inlet tube, 900 g of diethylene glycol dimethyl ether as a solvent, and t-butylperoxy 2-ethylhexanoate as a polymerization initiator (Nichiyu (Co.) Manufacture, brand name: 21.4 g of perbutyl O) was added, and it heated at 90 degreeC. 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., brand name; Flaxel FM1) were added to the bis, which is a polymerization initiator. It was added dropwise over 3 hours with 21.4 g of (4-t-butylcyclohexyl) peroxydicarbonate (manufactured by Nichiyu Co., Ltd., brand name; Peroyl TCP) over 3 hours. By further aging this for 6 hours, a carboxyl group-containing copolymer resin was obtained. In addition, this reaction was performed in a nitrogen atmosphere.

Then, to the obtained copolymer resin containing a carboxyl group, 3,4-epoxycyclohexylmethylacrylate (manufactured by Daicel, brand name; Cychroma A200) 363.9 g, dimethylbenzylamine 3.6 g as a ring-opening catalyst, hydroquinone mono as a polymerization inhibitor 1.80 g of methyl ether was added, it heated at 100 degreeC, and this was stirred, and the ring-opening addition reaction of epoxy was performed. After 16 hours, a solution containing 53.8 mass% (non-volatile content) of a carboxyl group-containing resin having an acid value of 108.9 mgKOH/g and a mass average molecular weight of 25,000 was obtained.

[Synthesis Example 2]

(Varnish 2)

To a flask equipped with a thermometer, stirrer, dropping funnel and reflux condenser, diethylene glycol monoethyl ether acetate as a solvent and azobisisobutyronitrile as a catalyst were added, and this was heated to 80° C. under a nitrogen atmosphere, and methacryl A monomer obtained by mixing an acid and methyl methacrylate at a molar ratio of 0.40:0.60 was added dropwise over about 2 hours. After stirring this for an additional hour, the temperature was raised to 115° C. and deactivated to obtain a resin solution.

After cooling this resin solution, using tetrabutylammonium bromide as a catalyst, adding butyl glycidyl ether at a molar ratio of 0.40 at 95 to 105°C for 30 hours, and the same amount of the carboxyl group of the obtained resin and addition reaction And cooled.

In addition, tetrahydrophthalic anhydride was added to the OH group of the resin obtained above at 95 to 105°C for 8 hours at a molar ratio of 0.26. This was taken out after cooling to obtain a solution containing 50% by mass (non-volatile content) of a carboxyl group-containing resin having a solid content of 78.1 mgKOH/g and a mass average molecular weight of 35,000.

[Synthesis Example 3]

(Varnish 3)

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

[Preparation of cellulose nanofiber dispersion]

Cellulose nanofibers (BiNFi-s (bean piece) manufactured by Sugino Machine Co., Ltd., 10% by mass cellulose, number average fiber diameter of 80 nm) were dehydrated and filtered, and carbitol acetate of 10 times the weight of the filtrate was added. After stirring for a minute, it was filtered. This substitution operation was repeated three times, and a 10-fold amount of carbitol acetate was added to the filtrate to prepare a 10 mass% cellulose nanofiber dispersion.

<Example 1>

* 1-1) Thermosetting compound 1: Epicoat 828 manufactured by Mitsubishi Chemical Co., Ltd.

* 1-2) Thermosetting compound 2: Epicoat 807 manufactured by Mitsubishi Chemical Co., Ltd.

* 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 Chemie Japan Co., Ltd.

* 1-5) Acrylic copolymer compound 2: Polyflow No.50EHF (solid content 50% by mass) manufactured by Kusumoto Kasei Co., Ltd.

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

* 1-7) Colorant: Phthalocyanine Blue

* 1-8) Organic Solvent: Carbitol Acetate

* 1-9) Thermosetting compound 3: Unidic V-8000 (solid content 40% by mass) manufactured by DIC Corporation

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

* 1-11) Curing catalyst 2: triphenylphosphine

* 1-12) Photocurable compound 1: Bisphenol A type epoxy acrylate manufactured by Mitsubishi Chemical Co., Ltd.

* 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 manufactured by Kyoesha Chemical Co., Ltd.

* 1-16) Photoinitiator 1: 2-ethylanthraquinone

* 1-17) Thermoplastic resin 1: Novatech PP BC03L manufactured by Nippon Polypro Co., Ltd.

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

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

[Preparation of the composition]

Examples 1-1 to 1-12 and Comparative Examples 1-1 to 1-3 in Tables 1 and 2, and Examples 1-19 to 1-21 and Comparative Examples in Table 4 For 1-6, each component was blended, stirred, and dispersed with a triaxial roll to prepare a composition, respectively.

[Production of composite molded body]

For Examples 1-13 to Examples 1-15 and Comparative Example 1-4 in Table 3 above, after mixing each component, 180 using a kneader (Labo Plasto Mill, Toyo Seki Co., Ltd.) It melt-kneaded at a rotational speed of 70 rpm for 10 minutes at degreeC. Using a press machine (Labo Press P2-30T, manufactured by Toyo Seki Co., Ltd.), the obtained kneaded product was hot pressed at 190°C for 3 minutes at 0.5 MPa and for 1 minute at 20 MPa, and further 23°C and 0.5 MPa. It cold-pressed over 1 minute with a furnace. Thereby, a sheet-like cellulose nanofiber composite molded article having a thickness of 0.05 mm was obtained.

For Examples 1-16 to 1-18 and Comparative Example 1-5 in Table 3, after mixing each component, 150 using a kneader (Labo Plasto Mill, Toyo Seki Co., Ltd.) It melt-kneaded at a rotational speed of 70 rpm for 10 minutes at degreeC. Using a press machine (Labo Press P2-30T, manufactured by Toyo Seki Co., Ltd.), the obtained kneaded product was hot pressed at 160°C for 3 minutes at 0.5 MPa and 1 minute at 20 MPa, and further 23°C and 0.5 MPa It cold-pressed over 1 minute with a furnace. Thereby, a sheet-like cellulose nanofiber composite molded article having a thickness of 0.05 mm was obtained.

(Preparation of test piece for evaluating smear removal property)

In Fig. 2, an explanatory diagram showing a method of manufacturing a substrate for evaluating smear removal is shown. In the drawing, (a) to (c-1) are plan views, and (c-2) is a cross-sectional view of (c-1). As shown in FIG. 2, the compositions of Examples 1-1 to 1-6 and Comparative Example 1-1 were formed with a conductor layer 13a on the insulating layer 13b, having a thickness of 50 mm×50 mm. A 1.6mm FR-4 copper clad laminate (copper pad equipped, copper thickness 18㎛) was printed on the entire surface by screen printing and cured in a hot air circulation drying furnace at 140℃ for 30 minutes. , An insulating resin layer 14 was formed. Next, a hole (via) 15 having a diameter of 100 μm was formed on the conductor layer 13a with a carbon dioxide gas laser to prepare a test piece.

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

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

Examples 1-13 to 1-18, Comparative Examples 1-4 and Comparative Example 1-5, the cellulose nanofiber composite molded body having a thickness of 0.05 mm was heated on the test substrate at 190°C and 20 MPa for 1 minute. A test piece was produced in the same manner as described above, except that it was pressed and further cold pressed at 23°C and 0.5 MPa over 1 minute to form an insulating resin layer.

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

(Smear removal)

Each test piece was immersed in a mixture of CircuPosit MLB conditioner 211 (Rohm & Haas, 200 ml/l) and CircuPosit Z (Rom & Haas, 100 ml/l) as a swelling liquid at 80°C for 5 minutes, Subsequently, as a roughening solution, it was immersed in a mixture of CircuPosit MLB promoter 213A (manufactured by Rohm and Haas, 100 ml/l) and Circupposit MLB promoter 213B (manufactured by Rohm and Haas, 150 ml/l) at 80°C for 10 minutes, Finally, it was immersed in CircuPosit MLB Neutralizer 216-2 (manufactured by Rohm and Haas, 200 ml/l) as a neutralizing solution at 50° C. for 5 minutes. Thereafter, the via bottom (copper surface) was observed with a scanning electron microscope (SEM, JSM-6610LV manufactured by Nihon Denshi Co., Ltd., magnification: 3,500 times), and the presence or absence of smear on the via bottom (copper surface) was visually checked. I did. The evaluation criteria are as follows. The evaluation results are shown in Tables 5 and 6 below.

(evaluation)

○: No smear

×: There is smear

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

Each test piece was prepared by forming an insulating resin layer on a test substrate of a FR-4 copper clad laminate (copper thickness of 18 µm) having a size of 50 mm x 50 mm and a thickness of 1.6 mm. The insulating resin layer was formed under the same conditions as the base material of the test piece for evaluating the smear removal property.

(Heat resistance)

After applying the rosin-based flux using each of the test pieces, it was flowed for 30 seconds in a solder bath set at 260°C in advance, washed with propylene glycol monomethyl ether acetate, dried, and then subjected to a peel test with a cellophane adhesive tape, 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 all in the coating film

X: Peeling occurred in the coating film

(Acid resistance)

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

(Pencil hardness)

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

(Preparation of test piece for electric insulation evaluation)

Using an FR-4 copper clad laminate (copper thickness of 18 µm) with a size of 100 mm x 150 mm and a thickness of 1.6 mm, a pattern of comb-shaped electrodes having an IPC standard B pattern was produced by an etching method, and a test substrate was obtained. Each test piece was produced by forming an insulating resin layer on the test substrate so as to cover the comb-shaped electrode portion. The insulating resin layer was formed under the same conditions as the base material of the test piece for evaluating the smear removal property.

(Electrical insulation)

Using each of the above test pieces, a DC500V bias was applied between the comb-shaped electrodes to measure the insulation resistance value. If the value is 100 GΩ or more, it is expressed as ○, and if it is less than 100 GΩ, it is expressed as × The results are shown in Tables 5 and 6 below.

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

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

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

A sheath having a width of 10 mm and a length of 100 mm was put in the plating layer of each test piece, and this end was peeled and held by a gripping member, and the load was measured when 35 mm was peeled in the vertical direction at a rate of 50 mm/min at room temperature. If it was 0.8 kN/m or more, it was set as ○, and if it was less than 0.8 kN/m, it was set as x. The results are shown in Tables 5 and 6 below.

As described in detail above, according to the printed wiring board material of the present invention, it is understood that smear on the upper surface of a metal foil such as copper is less likely to occur, and even if it occurs, it is easy to remove. Further, it was 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]

According to the description in Table 7 below, each component was blended, stirred, and dispersed with a triaxial roll to prepare each composition. The amounts of the cellulose nanofibers and the layered silicate added were 10% by mass, respectively, with respect to the total amount of the composition excluding the solvent. Next, this composition was printed on the entire surface by a screen printing method on a copper foil having a thickness of 18 μm, and cured in a hot air circulation drying furnace at 140° C. for 30 minutes. After that, the copper foil was removed to prepare a 50 µm-thick sheet.

[Evaluation of linear expansion coefficient]

The sheet produced above was cut into 3 mm width x 30 mm length. This was heated at 5°C/min from room temperature to 200°C in a tension mode, 10 mm between chuck, load 30mN, and nitrogen atmosphere using SII TMA (Thermomechanical Analysis) “EXSTAR6000”, and then, The temperature was lowered from 200°C to 20°C at 5°C/min. Then, the linear expansion coefficient was calculated|required from the measurement value of 30 degreeC to 100 degreeC when the temperature was raised from 20 degreeC to 200 degreeC at 5 degreeC/min. The evaluation results are shown in Table 7.

* 2-1) Thermosetting compound 1: Epicoat 828 manufactured by Mitsubishi Chemical Co., Ltd.

* 2-2) Thermosetting compound 2: Epicoat 807 manufactured by Mitsubishi Chemical Co., Ltd.

* 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

According to the description in Table 8 below, each component was blended, stirred, and dispersed with a triaxial roll to prepare each composition. The amounts of the cellulose nanofibers and the layered silicate added were 10% by mass, respectively, with respect to the total amount of the composition excluding the solvent. Subsequently, this composition was printed on the entire surface by a screen printing method on a copper foil having a thickness of 18 μm, dried in a hot air circulation drying furnace at 100°C for 30 minutes, and then cured at 170°C for 60 minutes. . Then, the copper foil was removed, and the linear expansion coefficient of the obtained sheet|seat of 50 micrometers was measured.

* 2-7) Thermosetting compound 3: Unidic V-8000 (solid content 40% by mass) manufactured by DIC Corporation

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

* 2-9) Curing catalyst 2: triphenylphosphine

According to the description in Table 9 below, each component was blended, and melt-kneaded at 180°C for 10 minutes at 180°C using a kneader (Labo Plastomill, manufactured by Toyo Seki Co., Ltd.). The amounts of the cellulose nanofibers and the layered silicate added were 10% by mass, respectively, with respect to the total amount of the composition excluding the solvent. Using a press machine (Labo Press P2-30T, manufactured by Toyo Seki Co., Ltd.), the obtained kneaded product was hot pressed at 190°C for 3 minutes at 0.5 MPa and for 1 minute at 20 MPa, and further 23°C and 0.5 MPa. It cold-pressed over 1 minute with a furnace. Thus, the coefficient of linear expansion of the obtained sheet having a thickness of 50 µm was measured.

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

According to the description in Table 10 below, each component was blended, and melt-kneaded at 150°C for 10 minutes at 150°C using a kneader (Labo Plasto Mill, manufactured by Toyo Seki Co., Ltd.). The amounts of the cellulose nanofibers and the layered silicate added were 10% by mass, respectively, with respect to the total amount of the composition excluding the solvent. Using a press machine (Labo Press P2-30T, manufactured by Toyo Seki Co., Ltd.), the obtained kneaded product was hot pressed at 160°C for 3 minutes at 0.5 MPa and 1 minute at 20 MPa, and further 23°C and 0.5 MPa It cold-pressed over 1 minute with a furnace. Thus, the coefficient of linear expansion of the obtained sheet having a thickness of 50 µm was measured.

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

According to the description in Table 11 below, each component was blended, stirred, and dispersed with a triaxial roll to prepare each composition. The amounts of the cellulose nanofibers and the layered silicate added were 10% by mass, respectively, with respect to the total amount of the composition excluding the solvent. Subsequently, this composition was printed on the entire surface by a screen printing method on a copper foil having a thickness of 18 μm, dried in a hot air circulation drying furnace at 120° C. for 10 minutes, and then cured at 250° C. for 30 minutes. . Then, the copper foil was removed, and the linear expansion coefficient of the obtained sheet|seat of 50 micrometers was measured.

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

According to the description in Table 12 below, each component was blended, stirred, and dispersed with a triaxial roll to prepare each composition. The amounts of the cellulose nanofibers and the layered silicate added were 10% by mass, respectively, with respect to the total amount of the composition excluding the solvent. Next, this composition was printed on the entire surface by a screen printing method on a copper foil having a thickness of 18 µm, and cured by irradiating a cumulative amount of light of ² J/cm ² at a wavelength of 350 nm with a metal halide lamp. Thereafter, the copper foil was removed, and the coefficient of linear expansion of the obtained sheet having a thickness of 50 μm was measured.

* 2-13) Photocurable compound 1: Bisphenol A type epoxy acrylate manufactured by Mitsubishi Chemical Co., Ltd.

* 2-14) Photocurable compound 2: trimethylolpropane triacrylate

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

* 2-16) Photocurable compound 4: Light ester HO manufactured by Kyoesha Chemical Co., Ltd.

* 2-17) Photoinitiator 1: 2-ethylanthraquinone

According to the description in Tables 13 to 15 below, each component was blended, stirred, and dispersed with a triaxial roll to prepare each composition. The amounts of the cellulose nanofibers and the layered silicate added were 10% by mass, respectively, with respect to the total amount of the composition excluding the solvent. Next, this composition was printed on the entire surface by a screen printing method on a copper foil having a thickness of 18 μm, and dried at 80° C. for 30 minutes in a hot air circulation drying furnace. Subsequently, using a negative pattern capable of covering the edge of the test board, exposed with a cumulative amount of light of 700 mJ/cm ² by an exposure machine for printed wiring board HMW-680GW (manufactured by Oak Co., Ltd.), and 1% at 30°C. Using an aqueous sodium carbonate solution as a developer, it was developed for 60 seconds in a developing device for a printed wiring board, and the edge portion was removed. Subsequently, it was thermosetted at 150 degreeC for 60 minutes in a hot air circulation type drying furnace. Then, the copper foil was removed, and the linear expansion coefficient of the obtained sheet|seat of 50 micrometers was measured.

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

As described in detail above, according to the insulating material in which cellulose nanofibers and layered silicate were used in combination, it was confirmed that the coefficient of linear expansion was drastically reduced.

<Example 3>

* 3-1) Thermosetting compound 1: Epicoat 828 manufactured by Mitsubishi Chemical Co., Ltd.

* 3-2) Thermosetting compound 2: Epicoat 807 manufactured by Mitsubishi Chemical Co., Ltd.

* 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 Chemical 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 Corporation

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

* 3-10) Organic Solvent: Carbitol Acetate

* 3-11) Thermosetting compound 3: Unidic V-8000 (solid content 40% by mass) manufactured by DIC Corporation

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

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

* 3-14) Thermoplastic resin 1: Novatech PPBC03L manufactured by Nippon Polypro Co., Ltd.

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

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

* 3-17) Photocurable compound 1: bisphenol A type epoxy acrylate manufactured by Mitsubishi Chemical Co., Ltd.

* 3-18) Photocurable compound 2: trimethylolpropane triacrylate

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

* 3-20) Photocurable compound 4: Light ester HO manufactured by Kyoesha Chemical 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 Co., Ltd.

* 3-24) Curing catalyst 4: dicyandiamide

* 3-25) Photoinitiator 1: 2-ethylanthraquinone

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

According to the formulation in the above table (Excluding Example 3-14, Example 3-15, Example 3-22, Example 3-23, Comparative Example 3-3 and Comparative Example 3-4), each component was Blending and stirring were carried out to disperse with a triaxial roll to prepare a composition, respectively. In addition, numbers in the table represent parts by mass.

In Example 3-14, Example 3-22, and Comparative Example 3-3, each component was blended, and a kneader (Labo Plasto Mill, manufactured by Toyo Seki Co., Ltd.) was used for 10 minutes at 180°C, It was melt-kneaded at a rotational speed of 70 rpm. Using a press machine (Labo Press P2-30T, manufactured by Toyo Seki Co., Ltd.), the obtained kneaded product was hot pressed at 190°C for 3 minutes at 0.5 MPa and for 1 minute at 20 MPa, and further 23°C and 0.5 MPa. It cold-pressed over 1 minute with a furnace. Thereby, a sheet-like cellulose nanofiber composite molded article having a thickness of 0.5 mm and 0.05 mm was obtained.

In Example 3-15, Example 3-23, and Comparative Example 3-4, each component was blended, and a kneader (Labo Plasto Mill, manufactured by Toyo Seki Co., Ltd.) was used for 10 minutes at 150°C, It was melt-kneaded at a rotational speed of 70 rpm. Using a press machine (Labo Press P2-30T, manufactured by Toyo Seki Co., Ltd.), the obtained kneaded product was hot pressed at 160°C for 3 minutes at 0.5 MPa and 1 minute at 20 MPa, and further 23°C and 0.5 MPa It cold-pressed over 1 minute with a furnace. Thereby, a sheet-like cellulose nanofiber composite molded article having a thickness of 0.5 mm and 0.05 mm was obtained.

[Evaluation as interlayer insulating material]

(Production of test piece)

3 is an explanatory diagram showing a method of manufacturing a substrate for evaluation of an interlayer insulating material. In the drawing, (a) to (e-1) are plan views, and (e-2) is a cross-sectional view of (e-1). As shown in FIG. 3, the compositions of Examples 3-1 to 3-12 and Comparative Example 3-1 were formed with a conductor layer 21a on the insulating layer 21b, having a thickness of 50 mm×50 mm. A 1.6 mm FR-4 copper clad laminate (with copper pad, copper thickness 18 μm) was printed on the entire surface by screen printing and cured in a hot air circulation drying furnace at 140°C for 30 minutes. Then, the insulating resin layer 22 was formed. Subsequently, a hole (via) 23 having a diameter of 100 μm was formed on the conductor layer 21a with a carbon dioxide gas laser, and then smear was removed with an aqueous potassium permanganate solution, electroless copper plating, and then electrolytic copper plating. The plating layer 24 was formed on the entire surface. Further, a test piece was produced by forming the wiring pattern 26 by an etching method. Reference numeral 25 in the drawing denotes an etching resist pattern.

The compositions of Example 3-13, Example 3-21, and Comparative Example 3-2 were printed on the entire surface by screen printing on the test substrate, and dried under conditions of 100° C. and 30 minutes in a hot air circulation drying furnace. Then, it was cured at 170°C for 60 minutes. Next, a test piece was produced by forming a wiring pattern as described above.

The cellulose nanofiber composite molded article having a thickness of 0.05 mm including Examples 3-14, 3-15, Example 3-22, Example 3-23, Comparative Example 3-3, and Comparative Example 3-4 Was hot-pressed on the test substrate at 190°C and 20 MPa over 1 minute, and further cold-pressed at 23°C and 0.5 MPa over 1 minute. Next, a test piece was produced by forming a wiring pattern as described above.

The compositions of Examples 3-16, 3-24, and Comparative Examples 3-5 were printed on the entire surface of the test substrate by screen printing, and dried in a hot air circulation drying furnace at 120° C. for 10 minutes. Then, it was cured at 250° C. for 30 minutes. Next, a test piece was produced by forming a wiring pattern as described above.

The compositions of Examples 3-17, 3-25, and Comparative Example 3-6 were printed on the test substrate on the entire surface by a screen printing method, and ² J/cm ² was accumulated at a wavelength of 350 nm with a metal halide lamp. It was cured by irradiating the amount of light. Next, a test piece was produced by forming a wiring pattern as described above.

The compositions of Examples 3-18 to 3-20, Examples 3-26 to Example 3-28 and Comparative Examples 3-7 to 3-9 were printed on the entire surface by a screen printing method, and hot air It was dried at 80°C for 30 minutes in a circulation drying furnace. Then, using a negative pattern capable of covering the edge of the test board, exposed with an exposure machine for printed wiring board HMW-680GW (manufactured by Oak Manufacturing Co., Ltd.) with a cumulative amount of light of 700 mJ/cm ² , and 1% sodium carbonate at 30° C. Using the aqueous solution as a developer, it was developed for 60 seconds with a developing solution for a printed wiring board, and the edge portion was then thermally cured at 150° C. for 60 minutes in a hot air circulation drying furnace. Next, a test piece was produced by forming a wiring pattern as described above.

(Insulation reliability evaluation)

A DC voltage of 50 V was applied to the electrodes of the six test pieces, and the test was carried out in an atmosphere at 130°C and 85%. The insulation resistance was measured in the test tank, and the time that became one hundredth of the insulation resistance value 1 hour after the start of the test was recorded. That the insulation resistance value did not decrease even after 100 hours ended there. The results are shown in the following table.

[Evaluation as a core material]

(Production of cellulose nanofiber sheet)

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

(Example 3-29)

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

(Example 3-30)

Epicoat 828 manufactured by Mitsubishi Chemical Co., Ltd. 50 parts by mass, Epicoat 807 manufactured by Mitsubishi Chemical Co., Ltd. 50 parts by mass, acrylic copolymer compound (BYK-361N manufactured by Big Chemical Japan Co., Ltd.) 1 mass Part, 3 parts by mass of 2MZ-A manufactured by Shikoku Kasei Kogyo 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 obtain a resin solution Except having produced, a test piece was obtained in the same manner as in Example 3-29.

(Comparative Example 3-10)

50 parts by mass of Epicoat 828 manufactured by Mitsubishi Chemical Co., Ltd., 50 parts by mass of Epicoat 807 manufactured by Mitsubishi Chemical Corporation, 3 parts by mass of 2MZ-A manufactured by Shikoku Chemical Co., Ltd., and 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 blended and stirred to prepare a resin solution.

(Example 3-31)

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

(Example 3-32)

100 parts by mass of Unidic V-8000 manufactured by DIC Co., Ltd., 23 parts by mass of Denacol EX-830 manufactured by Nagase Chemtex Co., Ltd., an acrylic copolymer compound (BYK-361N manufactured by Big Chemical Japan, Ltd.) 1 part by mass, 1 part by mass of triphenylphosphine, 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. In the same manner as in Example 3-29, a test piece was obtained.

(Comparative Example 3-11)

100 parts by mass of Unidic V-8000 manufactured by DIC Corporation, 23 parts by mass of Denacol EX-830 manufactured by Nagase Chemtex Corporation, 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 mixture was mixed and stirred to prepare a resin solution.

(Example 3-33)

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

(Example 3-34)

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

(Comparative Example 3-12)

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

(Example 3-35)

A copper foil of 18 µm was superimposed on the front and back of the sheet-like cellulose nanofiber composite molded body of Example 3-14 having a thickness of 0.5 mm, and heated by a vacuum press at a temperature of 190°C and a pressure of 0.5 MPa for 1 minute. Next, as shown in (a) to (c) of Fig. 4, the laminated plate 21 including the insulating layer 21b in which the conductor layer 21a is formed on both sides thereof, by drilling, a drill diameter of 300 μm The through hole 27 was formed with a pitch of 5 mm. Thereafter, smear was removed with an aqueous potassium permanganate solution, followed by electroless copper plating treatment, and then electrolytic copper plating treatment to form the through hole 28. Next, as shown in FIGS. 5A to 5C, 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 the 0.5 mm-thick sheet of Example 3-22 was used.

(Comparative Example 3-13)

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

(Example 3-37)

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

(Example 3-38)

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

(Comparative Example 3-14)

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

(Insulation reliability evaluation)

A DC voltage of 50 V was applied to the electrodes of the six test pieces, and the test was carried out in an atmosphere at 130°C and 85%. Insulation resistance was measured in the test tank, and the time that became one hundredth of the insulation resistance value 1 hour after the start of the test was recorded. That the insulation resistance value did not decrease even after 100 hours ended there.

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

<Example 4>

[Preparation of cellulose fiber dispersion]

Softwood kraft pulp (NBKP) was mechanically treated with a high-pressure homogenizer, and the obtained cellulose fibers having a number average fiber diameter of 3 µm were added to water and sufficiently stirred to prepare an aqueous suspension of 10% by mass of cellulose fibers. This was filtered with dehydration, carbitol acetate in an amount of 10 times the weight of the filtrate was added, followed by stirring for 30 minutes, followed by filtration. This substitution operation was repeated three times, and a 10-fold amount of carbitol acetate was added to the filtrate to prepare a cellulose fiber dispersion of 10% by mass.

[evaluation]

According to the description in Tables 24 and 25 below, each component was blended, stirred, and dispersed with a triaxial roll to prepare each composition. The resulting composition was printed on the entire surface by screen printing on a 1.6 mm thick FR-4 copper-clad laminate (copper thickness 18 μm) in a size of 150 mm×100 mm, and cured in a hot air circulation drying furnace at 140° C. for 30 minutes. Made it. The film thickness after curing was 50 µm. After that, the surface of the cured product was roughened with an aqueous potassium permanganate solution, electroless copper plating and then electrolytic copper plating were applied to the entire surface to prepare an evaluation substrate. Load (peel strength) when a sheath of a portion having a width of 10 mm and a length of 100 mm is put in the copper plated portion, the one end portion is peeled and held by a holding member, and 35 mm is peeled in the vertical direction at a rate of 50 mm/min in room temperature Was measured.

* 4-1) Thermosetting compound 1: Epicoat 828 manufactured by Mitsubishi Chemical Co., Ltd.

* 4-2) Thermosetting compound 2: Epicoat 807 manufactured by Mitsubishi Chemical Co., Ltd.

* 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

According to the description in Tables 26 and 27 below, each component was blended, stirred, and dispersed with a triaxial roll to prepare each composition. The obtained composition was printed on the entire surface by screen printing on a 1.6 mm thick FR-4 copper-clad laminate (copper thickness 18 μm) in a size of 150 mm×100 mm, and dried in a hot air circulation drying furnace at 100° C. for 30 minutes. Then, it was cured at 170°C for 60 minutes. The film thickness after curing was 50 µm. Thereafter, the surface of the cured product was roughened with an aqueous potassium permanganate solution, and electroless copper plating and then electrolytic copper plating were applied to the entire surface to prepare an evaluation substrate. Load (peel strength) when a sheath of a portion having a width of 10 mm and a length of 100 mm is put in the copper plated portion, the one end portion is peeled and held by a holding member, and 35 mm is peeled in the vertical direction at a rate of 50 mm/min in room temperature Was measured.

* 4-6) Thermosetting compound 3: Unidic V-8000 (solid content 40% by mass) manufactured by DIC Corporation

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

* 4-8) Curing catalyst 2: triphenylphosphine

According to the description in the following Tables 28 and 29, each component was blended, and melt-kneaded at 180°C for 10 minutes at 180°C using a kneader (Labo Plastomill, manufactured by Toyo Seki Co., Ltd.). Using a press machine (Labo Press P2-30T, manufactured by Toyo Seki Co., Ltd.), the obtained kneaded product was hot pressed at 190°C for 3 minutes at 0.5 MPa and for 1 minute at 20 MPa, and further 23°C and 0.5 MPa. It cold-pressed over 1 minute with a furnace. As a result, a 50 µm-thick sheet was obtained. This sheet was heat-pressed over a period of 1 minute at 190°C and 20 MPa by hot pressing on a 1.6 mm-thick FR-4 copper-clad laminate (copper thickness of 18 μm) in a size of 150 mm×100 mm, and further 23° C., 0.5 A test piece was prepared by cold pressing with MPa over 1 minute. Thereafter, the surface of the cured product was roughened with an aqueous potassium permanganate solution, and electroless copper plating and then electrolytic copper plating were applied to the entire surface to prepare an evaluation substrate. Load (peel strength) when a sheath of a portion having a width of 10 mm and a length of 100 mm is put in the copper plated portion, the one end portion is peeled and held by a holding member, and 35 mm is peeled in the vertical direction at a rate of 50 mm/min in room temperature Was measured.

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

According to the description in Table 30 and Table 31 below, each component was blended, and melt-kneaded at 150°C for 10 minutes at 150°C using a kneader (Labo Plasto Mill, manufactured by Toyo Seki Co., Ltd.). Using a press machine (Labo Press P2-30T, manufactured by Toyo Seki Co., Ltd.), the obtained kneaded product was hot pressed at 160°C for 3 minutes at 0.5 MPa and 1 minute at 20 MPa, and further 23°C and 0.5 MPa It cold-pressed over 1 minute with a furnace. As a result, a 50 µm-thick sheet was obtained. This sheet was heat-pressed over a period of 1 minute at 190°C and 20 MPa by hot pressing on a 1.6 mm thick FR-4 copper-clad laminate (copper thickness 18 μm) in a size of 150 mm×100 mm, and further 23° C., 0.5 MPa. It cold-pressed over a furnace for 1 minute, and produced the test piece. Thereafter, the surface of the cured product was roughened with an aqueous potassium permanganate solution, and electroless copper plating and then electrolytic copper plating were applied to the entire surface to prepare an evaluation substrate. Load (peel strength) when a sheath of a portion having a width of 10 mm and a length of 100 mm is put in the copper plated portion, the one end portion is peeled and held by a holding member, and 35 mm is peeled in the vertical direction at a rate of 50 mm/min in room temperature Was measured.

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

According to the description in Table 32 and Table 33 below, each component was blended, stirred, and dispersed with a triaxial roll to prepare each composition. The resulting composition was printed on the entire surface by screen printing on a 1.6 mm thick FR-4 copper-clad laminate (copper thickness 18 μm) in a size of 150 mm×100 mm, and dried in a hot air circulation drying furnace at 120° C. for 10 minutes. Then, it was cured at 250° C. for 30 minutes. The film thickness after curing was 50 µm. Thereafter, the surface of the cured product was roughened with an aqueous potassium permanganate solution, and electroless copper plating and then electrolytic copper plating were applied to the entire surface to prepare an evaluation substrate. Load (peel strength) when a sheath of a portion having a width of 10 mm and a length of 100 mm is put in the copper plated portion, the one end portion is peeled and held by a holding member, and 35 mm is peeled in the vertical direction at a rate of 50 mm/min in room temperature Was measured.

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

In accordance with the description in Tables 34 and 35 below, each component was blended, stirred, and dispersed with a triaxial roll to prepare each composition. The obtained composition was printed on the entire surface by screen printing on a 1.6 mm thick FR-4 copper-clad laminate (copper thickness 18 μm) with a size of 150 mm×100 mm, and accumulated ² J/cm ² at a wavelength of 350 nm with a metal halide lamp. It was cured by irradiating the amount of light. The film thickness after curing was 50 µm. Thereafter, the surface of the cured product was roughened with an aqueous potassium permanganate solution, and electroless copper plating and then electrolytic copper plating were applied to the entire surface to prepare an evaluation substrate. Load (peel strength) when a sheath of a portion having a width of 10 mm and a length of 100 mm is put in the copper plated portion, the one end portion is peeled and held by a holding member, and 35 mm is peeled in the vertical direction at a rate of 50 mm/min in room temperature Was measured.

* 4-12) Photocurable compound 1: Bisphenol A type epoxy acrylate manufactured by Mitsubishi Chemical Co., Ltd.

* 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 manufactured by Kyoesha Chemical Co., Ltd.

* 4-16) Photoinitiator 1: 2-ethylanthraquinone

According to the description in Tables 36 to 41 below, each component was blended, stirred, and dispersed with a triaxial roll to prepare each composition. The obtained composition was printed on the entire surface by a screen printing method on a 1.6 mm thick FR-4 copper-clad laminate (copper thickness 18 μm) in a size of 150 mm×100 mm, and dried at 80° C. for 30 minutes in a hot air circulation drying furnace. Then, using a negative pattern capable of covering the edge of the test board, exposed with an exposure machine for printed wiring board HMW-680GW (manufactured by Oak Manufacturing Co., Ltd.) with a cumulative amount of light of 700 mJ/cm ² , and 1% sodium carbonate at 30° C. Using the aqueous solution as a developer, it was developed for 60 seconds in a developing device for printed wiring boards, and the edge portion was then thermally cured at 150 DEG C for 60 minutes in a hot air circulation drying furnace. The film thickness after curing was 50 µm. Thereafter, the surface of the cured product was roughened with an aqueous potassium permanganate solution, and electroless copper plating and then electrolytic copper plating were applied to the entire surface to prepare an evaluation substrate. Load (peel strength) when a sheath of a portion having a width of 10 mm and a length of 100 mm is put in the copper plated portion, the one end portion is peeled and held by a holding member, and 35 mm is peeled in the vertical direction at a rate of 50 mm/min in room temperature Was measured.

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

As described in detail above, by using an insulating material containing cellulose nanofibers having a number average fiber diameter of 3 nm or more and less than 1000 nm and cellulose fibers having a number average fiber diameter of 1 μm or more, it was confirmed that the peel strength is dramatically improved.

<Example 5>

[Preparation of cellulose nanofiber dispersion having carboxylate]

(Production Example 1)

5 g of softwood bleached kraft pulp (manufactured by Oji Paper Co., Ltd., water 50% by mass, Canadian standard free water (CSF) 550 ml, mainly in an absolute dry state having a number average fiber diameter of more than 1000 nm), 2,2,6,6-tetramethyl Piperidine-N-oxyl (TEMPO) 79 mg (0.5 mmol) and sodium bromide 515 mg (5 mmol) were added to 500 ml of an aqueous solution dissolved therein, followed by stirring until the pulp was uniformly dispersed. 18 ml of an aqueous sodium hypochlorite solution containing 5% of effective chlorine was added thereto, and the pH was adjusted to 10 with a 0.5N aqueous hydrochloric acid solution to initiate an oxidation reaction. During the reaction, the pH in the system was lowered, but a 0.5N aqueous sodium hydroxide solution was gradually added to adjust the pH to 10. After the reaction for 2 hours, it 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 obtain an aqueous dispersion having a pulp concentration of 2% by mass, and stirred and dispersed for 5 minutes with a rotary blade mixer. Since the viscosity of the slurry remarkably increased with stirring, distilled water was added little by little, stirring and dispersion was continued with a mixer until the solid content concentration became 0.2% by mass, thereby obtaining a transparent gel-like aqueous solution. This was observed by TEM, and it was confirmed that it was an aqueous dispersion of cellulose nanofibers having a carboxylate having a number average fiber diameter of 10 nm. The amount of carboxyl groups in the aqueous dispersion was 1.25 mmol/g.

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

(Production Example 2)

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

(Production Example 3)

2-carboxy-2,2,6,6-tetramethylpiperidine-N-oxyl (4) instead of 79 mg (0.5 mmol) of 2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO) -Carboxy-TEMPO) Except having used 101 mg (0.5 mmol), it carried out similarly to Production Example 1, and produced the cellulose nanofiber dispersion 3 which has a 10 mass% carboxylate. In addition, the amount of carboxyl groups in the aqueous dispersion was 1.16 mmol/g, and the number average fiber diameter of the cellulose nanofibers having a carboxylate was 10 nm.

[Preparation of cellulose nanofiber dispersion]

(Production Example 4)

A plate made of eucalyptus was pulverized using a cutter mill to produce wood powder having a square of 0.2 mm. Subsequently, this 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. After 50 times of distilled water was added and stirred, and mechanical pulverization using a disk mill was performed 15 times, distilled water was added and stirred so as to be 10% by mass, thereby obtaining cellulose nanofibers having a number average fiber diameter of 80 nm. This was filtered with dehydration, carbitol acetate of 10 times the weight of the filtrate was added, stirred for 30 minutes, and then filtered. This substitution operation was repeated three times, and carbitol acetate in an amount of 10 times the weight of the filtrate was added to prepare a cellulose nanofiber dispersion 1 of 10% by mass.

* 5-1) Thermosetting compound 1: Epicoat 828 manufactured by Mitsubishi Chemical Co., Ltd.

* 5-2) Thermosetting compound 2: Epicoat 807 manufactured by Mitsubishi Chemical Co., Ltd.

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

* 5-4) Colorant: Phthalocyanine Blue

* 5-5) Organic solvent: Carbitol acetate

* 5-6) Thermosetting compound 3: Unidic V-8000 manufactured by DIC Co., Ltd. (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: Soxir SOXR-OB varnish manufactured by Nippon Kodoshi Kogyo Co., Ltd. (solid content 70% by mass, N-methylpyrrolidone 30% by mass)

* 5-10) Photocurable compound 1: Bisphenol A type epoxy acrylate manufactured by Mitsubishi Chemical Co., Ltd.

* 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 manufactured by Kyoesha Chemical Co., Ltd.

* 5-14) Photoinitiator 1: 2-ethylanthraquinone

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

* 5-16) Curing catalyst 4: dicyandiamide

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

* 5-18) Photocurable compound 5: dipentaerythritol tetraacrylate

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

[Production of sheet for evaluation of breaking strength and breaking elongation]

According to the description in Table 42, each component was blended, stirred, and dispersed with a triaxial roll to prepare each composition. Next, this composition was printed on the entire surface by a screen printing method on a copper foil having a thickness of 18 μm, and cured in a hot air circulation drying furnace at 140° C. for 30 minutes. After that, the copper foil was removed, and a 50 µm-thick evaluation sheet was produced.

According to the description in Table 43, each component was blended, stirred, and dispersed with a triaxial roll to prepare each composition. Subsequently, this composition was printed on the entire surface by a screen printing method on a copper foil having a thickness of 18 μm, dried in a hot air circulation drying furnace at 100°C for 30 minutes, and then cured at 170°C for 60 minutes. . After that, the copper foil was removed, and a 50 µm-thick evaluation sheet was produced.

According to the description of Table 44, each component was blended, stirred, and dispersed with a triaxial roll to prepare each composition. Subsequently, this composition was printed on the entire surface by a screen printing method on a copper foil having a thickness of 18 μm, dried in a hot air circulation drying furnace at 120° C. for 10 minutes, and then cured at 250° C. for 30 minutes. . Thereafter, the copper foil was removed to prepare a 50 µm-thick evaluation sheet.

According to the description of Table 45, each component was blended, stirred, and dispersed with a triaxial roll to prepare each composition. Next, this composition was printed on the entire surface by a screen printing method on a copper foil having a thickness of 18 µm, and cured by irradiating a cumulative amount of light of ² J/cm ² at a wavelength of 350 nm with a metal halide lamp. Thereafter, the copper foil was removed to prepare a 50 µm-thick evaluation sheet.

According to the description in Tables 46 to 48, each component was blended, stirred, and dispersed with a triaxial roll to prepare each composition. Next, this composition was printed on the entire surface by a screen printing method on a copper foil having a thickness of 18 μm, and dried at 80° C. for 30 minutes in a hot air circulation drying furnace. Then, using a negative pattern capable of covering the central part of the copper foil, it was exposed with a cumulative amount of light of 700 mJ/cm ² by an exposure machine HMW-680GW for a printed wiring board (manufactured by Oak Manufacturing Co., Ltd.), and 1% at 30°C. Using an aqueous sodium carbonate solution as a developer, it was developed for 60 seconds with a developer for a printed wiring board, and the copper foil edge was removed. Subsequently, it was cured at 150° C. for 60 minutes in a hot air circulation drying furnace. Thereafter, the copper foil was removed to prepare a 50 µm-thick evaluation sheet.

[Evaluation of breaking strength and breaking elongation]

According to JIS K7127, the evaluation sheet was cut into a predetermined size to prepare a test piece. This test piece was measured for breaking strength [MPa] and breaking elongation [%] at a tensile speed of 10 mm/min using a tensile tester (AGS-G manufactured by Shimadzu Corporation), and then based on the following evaluation criteria And evaluated. The results are shown in Tables 49 to 52 below. When both of the evaluation criteria for breaking strength and breaking elongation are ○, it can be seen that the cured product of the test piece has high toughness and is excellent in crack resistance.

(Evaluation criteria for breaking strength)

○: 75 MPa or more

△: 50 MPa or more and less than 75 MPa

×: less than 50 MPa

(Evaluation criteria for breaking elongation)

○: 6% or more

△: 4% or more and less than 6%

×: less than 4%

[Preparation of substrate for crack resistance evaluation]

In the production of the above breaking strength and breaking elongation evaluation sheet, the same applies except that a cured product having a thickness of 20 μm was obtained by using a 1.6 mm thick FR-4 copper clad laminate (copper thickness 18 μm) instead of copper foil. Through the process of, an evaluation substrate in which a cured product was formed on a copper clad laminate was produced.

[Evaluation of crack resistance]

The evaluation substrate was set to 1 cycle at -65°C for 30 minutes and 150°C for 30 minutes to give a temperature history of 1000 cycles, and the degree of cracking and peeling of the evaluation substrate after that was determined by an optical microscope ((Note ) It was observed 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 cracking

△: There is a crack

×: occurrence of crack is remarkable

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

<Example 6>

[Preparation of Lignocellulose Nanofiber Dispersion]

(Production Example 1)

A plate made of eucalyptus was pulverized using a cutter mill to produce wood powder having a square of 0.2 mm. Next, distilled water 50 times the mass of the wood powder was added and stirred, and after 15 times mechanical pulverization using a disk mill was performed, distilled water was added and stirred so as to be 10% by mass, and cellulose having a number average fiber diameter of 80 nm A nanofiber was obtained. This was filtered with dehydration, carbitol acetate of 10 times the weight of the filtrate was added, stirred for 30 minutes, and then filtered. This substitution operation was repeated three times, and carbitol acetate in an amount of 10 times the weight of the filtrate was added to prepare a lignocellulosic nanofiber dispersion 1 of 10% by mass.

(Production Example 2)

The board made of cedar was pulverized using a cutter mill to produce wood powder of about 0.2 mm square. Next, distilled water 50 times the mass of the wood powder was added and stirred, and after 15 times mechanical pulverization using a disk mill was performed, distilled water was added and stirred so as to be 10% by mass, and cellulose having a number average fiber diameter of 80 nm A nanofiber was obtained. This was filtered with dehydration, carbitol acetate of 10 times the weight of the filtrate was added, stirred for 30 minutes, and then filtered. This substitution operation was repeated three times, and carbitol acetate in an amount of 10 times the weight of the filtrate was added to prepare a lignocellulose nanofiber dispersion 2 of 10% by mass.

[Preparation of Comparative Cellulose Nanofiber Dispersion]

(Production Example 3)

A plate made of eucalyptus was pulverized using a cutter mill to produce wood powder having a square of 0.2 mm. Next, this wood flour was subjected to high temperature and high pressure treatment in an aqueous solution such as sodium sulfite or sodium hydroxide to remove lignin. After 50 times of distilled water was added and stirred to this, and mechanical pulverization using a disk mill was performed 15 times, distilled water was added and stirred so as to be 10% by mass to obtain cellulose nanofibers having a number average fiber diameter of 80 nm. This was filtered with dehydration, carbitol acetate of 10 times the weight of the filtrate was added, stirred for 30 minutes, and then filtered. This substitution operation was repeated three times, and carbitol acetate in an amount of 10 times the weight of the filtrate was added to prepare a cellulose nanofiber dispersion 1 of 10% by mass.

[Manufacture of printed wiring board material]

According to the description in the following Tables 53, 54 and 57 to 61, each component was blended, stirred, and dispersed with a triaxial roll to prepare each composition. In addition, all numbers in the following table represent mass parts.

According to the description in Table 55 below, each component was blended, and melt-kneaded at 180°C for 10 minutes at 180°C using a kneader (Labo Plastomill, manufactured by Toyo Seki Co., Ltd.). Using a press machine (Labo Press P2-30T, manufactured by Toyo Seki Co., Ltd.), the obtained kneaded product was hot pressed at 190°C for 3 minutes at 0.5 MPa and 20 MPa for 1 minute, and further at 23°C and 0.5 MPa. It was cold pressed over 1 minute. Thereby, sheet-like cellulose nanofiber composite molded bodies having a thickness of 0.5 mm and 0.05 mm were obtained, respectively.

According to the description in Table 56 below, each component was blended, and melt-kneaded at 150°C for 10 minutes at a rotation speed of 70 rpm using a kneader (Labo Plasto Mill, manufactured by Toyo Seki Co., Ltd.). Using a press machine (Labo Press P2-30T, manufactured by Toyo Seki Co., Ltd.), the obtained kneaded product was hot pressed at 160°C at 0.5 MPa for 3 minutes and at 20 MPa for 1 minute, and further at 23°C and 0.5 MPa. It was cold pressed over 1 minute. Thereby, sheet-like cellulose nanofiber composite molded bodies having a thickness of 0.5 mm and 0.05 mm were obtained, respectively.

* 6-1) Thermosetting compound 1: Epicoat 828 manufactured by Mitsubishi Chemical Co., Ltd.

* 6-2) Thermosetting compound 2: Epicoat 807 manufactured by Mitsubishi Chemical Co., Ltd.

* 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: Unidic V-8000 manufactured by DIC Co., Ltd. (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: Novatech PP BC03L manufactured by Nippon Polypro Co., Ltd.

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

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

* 6-12) Photocurable compound 1: Bisphenol A type epoxy acrylate manufactured by Mitsubishi Chemical Co., Ltd.

* 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 manufactured by Kyoesha Chemical Co., Ltd.

* 6-16) Photoinitiator 1: 2-ethylanthraquinone

* 6-17) Curing catalyst 3: Finely pulverized melamine (manufactured by Nissan Chemical Co., Ltd.)

* 6-18) Curing catalyst 4: Dicyandiamide

* 6-19) Photoinitiator 2: Irgacure 907 (manufactured by BASF)

* 6-20) Photocurable compound 5: dipentaerythritol tetraacrylate

* 6-21) Thermosetting compound 5: TEPIC-H (manufactured by Nissan Chemical Co., Ltd.)

[Evaluation as a solder resist]

(Preparation of test board)

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

On the test substrate, the compositions of Examples 6-1 to 6-6 and Comparative Examples 6-1 and 6-2 were printed by screen printing so that the comb-shaped electrode was covered, and 140° C. in a hot air circulation drying furnace, It was cured under the condition of 30 minutes to prepare a test piece.

As the withstand voltage test, a DC voltage was applied to each of the six test pieces at a boosting speed of 500 V per second, and the voltage to be destroyed was measured. A case in which the average of 6 sheets was 4.5 kV or more was evaluated as ○, and a case in which it was less than 4.5 kV was evaluated as x. As for the result, all of Example 6-1 to Example 6-6 were ○, and all of Comparative Examples 6-1 and 6-2 were ×.

In addition, as an insulation reliability test, a DC voltage of 50 V was applied to each of six test pieces, and a stand-alone test was performed in an atmosphere of 130°C and 85% RH, and the time until short-circuit was measured. A case in which the average of 6 sheets was 200 hours or more was evaluated as ○, and a case in which it was less than 200 hours was evaluated as x. As for the result, all of Example 6-1 to Example 6-6 were ○, and all of Comparative Examples 6-1 and 6-2 were ×.

On the test substrate, the compositions of Examples 6-7 to 6-12 and Comparative Examples 6-3 and 6-4 were printed by screen printing so that the comb-shaped electrode was covered, and at 100° C. in a hot air circulation drying furnace, After drying under the conditions of 30 minutes, it was cured under the conditions of 170°C and 60 minutes to prepare a test piece.

As the withstand voltage test, a DC voltage was applied to each of the six test pieces at a boosting speed of 500 V per second, and the voltage to be destroyed was measured. A case in which the average of 6 sheets was 5.5 kV or more was evaluated as ○, and a case in which the average of 6 sheets was less than 5.5 kV was evaluated as x. As a result, all of Examples 6-7 to 6-12 were ○, and all of Comparative Examples 6-3 and 6-4 were ×.

In addition, as an insulation reliability test, a DC voltage of 50 V was applied to each of six test pieces, and a stand-alone test was performed in an atmosphere of 130°C and 85% RH, and the time until short-circuit was measured. The case where the average of 6 sheets was 300 hours or more was evaluated as ○, and the case of less than 300 hours was evaluated as ×. As for the result, all of Examples 6-7 to 6-12 were ○, and all of Comparative Examples 6-3 and 6-4 were ×.

On the test substrate, sheets having a thickness of 0.05 mm of Examples 6-13 to 6-24 and Comparative Examples 6-5 to 6-8 were cut out so that the comb-shaped electrodes were covered, and 190°C by hot pressing. Then, it hot-pressed over 1 minute at 20 MPa, and further cold-pressed at 23 degreeC and 0.5 MPa over 1 minute, and produced the test piece.

As the withstand voltage test, a DC voltage was applied to each of the six test pieces at a boosting speed of 500 V per second, and the voltage to be destroyed was measured. A case in which the average of 6 sheets was 3.5 kV or more was evaluated as ○, and a case in which the average of 6 sheets was less than 3.5 kV was evaluated as x. As for the result, all of Examples 6-13 to 6-24 were ○, and all of Comparative Examples 6-5 to 6-8 were ×.

In addition, as an insulation reliability test, a DC voltage of 50 V was applied to each of six test pieces, and a stand-alone test was performed in an atmosphere of 130°C and 85% RH, and the time until short-circuit was measured. A case in which the average of 6 sheets was 250 hours or more was evaluated as ○, and a case in which it was less than 250 hours was evaluated as x. As for the result, all of Examples 6-13 to 6-24 were ○, and all of Comparative Examples 6-5 to 6-8 were ×.

On the test substrate, the compositions of Examples 6-25 to 6-30 and Comparative Examples 6-9 and 6-10 were printed by screen printing so that the comb-shaped electrode was covered, and 120° C. in a hot air circulation drying furnace, After drying under the conditions of 10 minutes, it was cured at 250°C for 30 minutes to prepare a test piece.

As the withstand voltage test, a DC voltage was applied to each of the six test pieces at a boosting speed of 500 V per second, and the voltage to be destroyed was measured. A case in which the average of 6 sheets was 5.5 kV or more was evaluated as ○, and a case in which the average of 6 sheets was less than 5.5 kV was evaluated as x. As for the result, all of Examples 6-25 to 6-30 were ○, and all of Comparative Examples 6-9 and 6-10 were ×.

In addition, as an insulation reliability test, a DC voltage of 50 V was applied to each of the six test pieces, and a stand-alone test was performed in an atmosphere of 130° C. and 85% RH, and the time until short-circuited was measured. A case in which the average of 6 sheets was 250 hours or more was evaluated as ○, and a case in which it was less than 250 hours was evaluated as x. As for the result, all of Examples 6-25 to 6-30 were ○, and all 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 screen printing so that the comb-shaped electrode was covered, followed by a metal halide lamp at a wavelength of 350 nm. By irradiating and curing the accumulated light amount of ² J/cm ² , a test piece was prepared.

As the withstand voltage test, a DC voltage was applied to each of the six test pieces at a boosting speed of 500 V per second, and the voltage to be destroyed was measured. A case in which the average of 6 sheets was 3.5 kV or more was evaluated as ○, and a case in which the average of 6 sheets was less than 3.5 kV was evaluated as x. As for the result, all of Examples 6-31 to 6-36 were ○, and all of Comparative Examples 6-11 and 6-12 were ×.

In addition, as an insulation reliability test, a DC voltage of 50 V was applied to each of six test pieces, and a stand-alone test was performed in an atmosphere of 130°C and 85% RH, and the time until short-circuit was measured. The case where the average of 6 sheets was 100 hours or more was evaluated as ○, and the case of less than 100 hours was evaluated as ×. As for the result, all of Examples 6-31 to 6-36 were ○, and all 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 screen printing using a 100 mesh polyester bias plate, , In a hot air circulation drying furnace, it was dried at 80°C for 30 minutes. Then, using a negative pattern that can be covered by the comb-shaped electrode, it was exposed with a cumulative amount of 700mJ/cm ² with an exposure machine for printed wiring board HMW-680GW (manufactured by Oak Co., Ltd.), and a 1% sodium carbonate aqueous solution at 30°C As a developer, it was developed for 60 seconds with a developing solution for a printed wiring board, followed by thermosetting at 150° C. for 60 minutes in a hot air circulation drying furnace to prepare a test piece.

As the withstand voltage test, a DC voltage was applied to each of the six test pieces at a boosting speed of 500 V per second, and the voltage to be destroyed was measured. A case in which the average of 6 sheets was 4.5 kV or more was evaluated as ○, and a case in which it was less than 4.5 kV was evaluated as x. As a result, all of Examples 6-37 to 6-54 were ○, and all of Comparative Examples 6-13 to 6-18 were ×.

In addition, as an insulation reliability test, a DC voltage of 50 V was applied to each of six test pieces, and a stand-alone test was performed in an atmosphere of 130°C and 85% RH, and the time until short-circuit was measured. A case in which the average of 6 sheets was 200 hours or more was evaluated as ○, and a case in which it was less than 200 hours was evaluated as x. As a result, all of Examples 6-37 to 6-54 were ○, and all of Comparative Examples 6-13 to 6-18 were ×.

[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 a 1.6 mm thick FR-4 copper-clad laminate (copper thickness 9 μm) with a size of 100 mm×150 mm, and a screen It was printed on the entire surface by a printing method, and cured in a hot air circulation drying furnace at 140°C for 30 minutes. Next, electroless copper plating was performed, and then electrolytic copper plating was performed. Thereafter, a test piece having a pattern of comb-shaped electrodes of IPC standard B pattern was produced by an etching method.

As the withstand voltage test, a DC voltage was applied to each of the six test pieces at a boosting speed of 500 V per second, and the voltage to be destroyed was measured. A case in which the average of 6 sheets was 5.5 kV or more was evaluated as ○, and a case in which the average of 6 sheets was less than 5.5 kV was evaluated as x. As for the result, all of Example 6-1 to Example 6-6 were ○, and all of Comparative Examples 6-1 and 6-2 were ×.

In addition, as an insulation reliability test, a DC voltage of 50 V was applied to each of six test pieces, and a stand-alone test was performed in an atmosphere of 130°C and 85% RH, and the time until short-circuit was measured. A case in which the average of 6 sheets was 400 hours or more was evaluated as ○, and a case in which it was less than 400 hours was evaluated as x. As for the result, all of Example 6-1 to Example 6-6 were ○, and all of Comparative Examples 6-1 and 6-2 were ×.

The compositions of Examples 6-7 to 6-12 and Comparative Examples 6-3 and 6-4 were applied to a 1.6 mm thick FR-4 copper-clad laminate (copper thickness 9 μm) with a size of 100 mm×150 mm, and a screen It was printed on the entire surface by a printing method, dried at 100°C for 30 minutes in a hot air circulation drying furnace, and then cured at 170°C for 60 minutes. Next, electroless copper plating was performed, and then electrolytic copper plating was performed. Thereafter, a test piece having a pattern of comb-shaped electrodes of IPC standard B pattern was produced by an etching method.

As the withstand voltage test, a DC voltage was applied to each of the six test pieces at a boosting speed of 500 V per second, and the voltage to be destroyed was measured. A case in which the average of 6 sheets was 6.5 kV or more was evaluated as ○, and a case where the average of 6 sheets was less than 6.5 kV was evaluated as x. As for the result, all of Examples 6-7 to 6-12 were ○, and all of Comparative Examples 6-3 and 6-4 were ×.

In addition, as an insulation reliability test, a DC voltage of 50 V was applied to each of six test pieces, and a stand-alone test was performed in an atmosphere of 130°C and 85% RH, and the time until short-circuit was measured. The average of 6 sheets was evaluated as? For 500 hours or more, and x for less than 500 hours. As for the result, all of Examples 6-7 to 6-12 were ○, and all of Comparative Examples 6-3 and 6-4 were ×.

Examples 6-13 to 6-24 and Comparative Examples 6-5 to 6-8 were prepared by using a 0.05 mm thick FR-4 copper-clad laminate with a thickness of 100 mm x 150 mm and a thickness of 1.6 mm (copper thickness 9 µm) by hot pressing at 190°C and 20 MPa for 1 minute, followed by cold pressing at 23°C and 0.5 MPa for 1 minute. Next, electroless copper plating was performed, and then electrolytic copper plating was performed. Thereafter, a test piece having a pattern of comb-shaped electrodes of IPC standard B pattern was produced by an etching method.

As the withstand voltage test, a DC voltage was applied to each of the six test pieces at a boosting speed of 500 V per second, and the voltage to be destroyed was measured. A case in which the average of 6 sheets was 4.5 kV or more was evaluated as ○, and a case in which it was less than 4.5 kV was evaluated as x. As for the result, all of Examples 6-13 to 6-24 were ○, and all of Comparative Examples 6-5 to 6-8 were ×.

In addition, as an insulation reliability test, a DC voltage of 50 V was applied to each of six test pieces, and a stand-alone test was performed in an atmosphere of 130°C and 85% RH, and the time until short-circuit was measured. A case in which the average of 6 sheets was 400 hours or more was evaluated as ○, and a case in which it was less than 400 hours was evaluated as x. As for the result, all of Examples 6-13 to 6-24 were ○, and all of Comparative Examples 6-5 to 6-8 were ×.

The compositions of Examples 6-25 to 6-30 and Comparative Examples 6-9 and 6-10 were applied to a 1.6 mm thick FR-4 copper-clad laminate (copper thickness 9 μm) with a size of 100 mm×150 mm, and a screen It was printed on the entire surface by a printing method, dried at 120°C for 10 minutes in a hot air circulation drying furnace, and then cured at 250°C for 30 minutes. Next, electroless copper plating was performed, and then electrolytic copper plating was performed. Thereafter, a test piece having a pattern of comb-shaped electrodes of IPC standard B pattern was produced by an etching method.

As the withstand voltage test, a DC voltage was applied to each of the six test pieces at a boosting speed of 500 V per second, and the voltage to be destroyed was measured. A case in which the average of 6 sheets was 6 kV or more was evaluated as ?, and a case in which the average of 6 sheets was less than 6 kV was evaluated as x. As for the result, all of Examples 6-25 to 6-30 were ○, and all of Comparative Examples 6-9 and 6-10 were ×.

In addition, as an insulation reliability test, a DC voltage of 50 V was applied to each of six test pieces, and a stand-alone test was performed in an atmosphere of 130°C and 85% RH, and the time until short-circuit was measured. A case in which the average of 6 sheets was 400 hours or more was evaluated as ○, and a case in which it was less than 400 hours was evaluated as x. As for the result, all of Examples 6-25 to 6-30 were ○, and all 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 applied to a 1.6 mm thick FR-4 copper-clad laminate (copper thickness 9 μm) with a size of 100 mm×150 mm, and a screen It printed on the entire surface by the printing method, and then cured by irradiating the accumulated light amount of ² J/cm ² at a wavelength of 350 nm with a metal halide lamp. Next, electroless copper plating was performed, and then electrolytic copper plating was performed. Thereafter, a test piece having a pattern of comb-shaped electrodes of IPC standard B pattern was produced by an etching method.

As the withstand voltage test, a DC voltage was applied to each of the six test pieces at a boosting speed of 500 V per second, and the voltage to be destroyed was measured. A case in which the average of 6 sheets was 4.5 kV or more was evaluated as ○, and a case in which it was less than 4.5 kV was evaluated as x. As for the result, all of Examples 6-31 to 6-36 were ○, and all of Comparative Examples 6-11 and 6-12 were ×.

In addition, as an insulation reliability test, a DC voltage of 50 V was applied to each of six test pieces, and a stand-alone test was performed in an atmosphere of 130°C and 85% RH, and the time until short-circuit was measured. A case in which the average of 6 sheets was 250 hours or more was evaluated as ○, and a case in which it was less than 250 hours was evaluated as x. As for the result, all of Examples 6-31 to 6-36 were ○, and all 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 applied to a 1.6 mm thick FR-4 copper-clad laminate (copper thickness 9 μm) with a size of 100 mm×150 mm. , By the screen printing method, a 100 mesh polyester bias plate was used, and the entire surface was printed and dried at 80°C for 30 minutes in a hot air circulation drying furnace. Subsequently, a transparent PET film was used in place of the negative pattern, exposed with a cumulative amount of 700 mJ/cm ² with an exposure machine for printed wiring board HMW-680GW (manufactured by Oak Co., Ltd.), and a 1% sodium carbonate aqueous solution at 30°C was used as a developer. As a result, it developed for 60 seconds with a developing device for printed wiring boards, and then thermally cured at 150° C. for 60 minutes in a hot air circulation drying furnace. Next, electroless copper plating was performed, and then electrolytic copper plating was performed. Thereafter, a test piece having a pattern of comb-shaped electrodes of IPC standard B pattern was produced by an etching method.

As the withstand voltage test, a DC voltage was applied to each of the six test pieces at a boosting speed of 500 V per second, and the voltage to be destroyed was measured. A case in which the average of 6 sheets was 5.5 kV or more was evaluated as ○, and a case in which the average of 6 sheets was less than 5.5 kV was evaluated as x. As a result, all of Examples 6-37 to 6-54 were ○, and all of Comparative Examples 6-13 to 6-18 were ×.

In addition, as an insulation reliability test, a DC voltage of 50 V was applied to each of six test pieces, and a stand-alone test was performed in an atmosphere of 130°C and 85% RH, and the time until short-circuit was measured. A case in which the average of 6 sheets was 400 hours or more was evaluated as ○, and a case in which it was less than 400 hours was evaluated as x. As a result, all of Examples 6-37 to 6-54 were ○, and all of Comparative Examples 6-13 to 6-18 were ×.

[Evaluation as a core material]

(Production of Lignocellulose Nanofiber Sheet)

For the lignocellulosic nanofiber dispersion 1 and the lignocellulosic nanofiber dispersion 2, a 0.2% by mass dispersion was prepared with carbitol acetate, filtered through a glass filter, and a sheet having a size of 100 mm×150 mm and a thickness of 40 μm was prepared. .

(Production of cellulose nanofiber sheet)

About the cellulose nanofiber dispersion liquid 1, a 0.2 mass% dispersion liquid was produced with carbitol acetate, and it filtered with a glass filter, and the size of 100 mm × 150 mm and a sheet having a thickness of 40 μm was produced.

Epicoat 828 manufactured by Mitsubishi Chemical Co., Ltd. 50 parts by mass, Epicoat 807 manufactured by Mitsubishi Chemical Co., Ltd. 50 parts by mass, 2MZ-A manufactured by Shikoku Chemical Co., Ltd. 3 parts by mass, methyl 100 parts by mass of ethyl ketone was blended and stirred to obtain a resin solution. This was impregnated into each cellulose nanofiber sheet, left to stand in an atmosphere at 50°C for 12 hours, then taken out and dried at 80°C for 5 hours to prepare a prepreg. Ten sheets of this prepreg were stacked, and a copper foil having a thickness of 18 µm was further stacked on the front and the back, and cured in a vacuum press at a temperature of 160°C and a pressure of 2 MPa for 3 hours. Thereafter, a test piece having a pattern of comb-shaped electrodes of IPC standard B pattern was produced by an etching method. The test piece of lignocellulosic nanofiber dispersion 1 was used in Example 6-55, the test piece of lignocellulosic nanofiber dispersion 2 was used in Example 6-56, and the test piece of cellulose nanofiber dispersion 1 was used in Comparative Example 6-19, instead of cellulose nanofibers. What was produced in the same manner as using glass fiber was used as Comparative Example 6-20. The filling ratio of the cellulose fibers of Examples 6-55, 6-56, Comparative Example 6-19, and Comparative Example 6-20 was 30% by mass. In addition, in Examples 6-55 and 6-56, 1 part by mass of an acrylic copolymer compound (BYK-361N manufactured by BIC Chem Japan Co., Ltd.) was added.

As the withstand voltage test, a DC voltage was applied to each of the six test pieces at a boosting speed of 500 V per second, and the voltage to be destroyed was measured. A case in which the average of 6 sheets was 5.5 kV or more was evaluated as ○, and a case in which the average of 6 sheets was less than 5.5 kV was evaluated as x. As for the result, all of Examples 6-55 and 6-56 were ○, and all of Comparative Examples 6-19 and 6-20 were ×.

In addition, as an insulation reliability test, a DC voltage of 50 V was applied to each of six test pieces, and a stand-alone test was performed in an atmosphere of 130°C and 85% RH, and the time until short-circuit was measured. A case in which the average of 6 sheets was 400 hours or more was evaluated as ○, and a case in which it was less than 400 hours was evaluated as x. As for the result, all of Examples 6-55 and 6-56 were ○, and all 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 Chemtex Corporation, 1 part by mass of triphenylphosphine, and 100 parts by mass of methyl ethyl ketone Blended and stirred to obtain a resin solution. This was impregnated into each cellulose nanofiber sheet, left to stand in an atmosphere at 50°C for 12 hours, then taken out and dried at 80°C for 5 hours to prepare a prepreg. Ten sheets of this prepreg were stacked, and 18 µm copper foil was further stacked on the front and the back, and cured with a vacuum press at a temperature of 160°C and a pressure of 2 MPa for 3 hours. Thereafter, a test piece having a pattern of comb-shaped electrodes of IPC standard B pattern was produced by an etching method. The test piece of lignocellulosic nanofiber dispersion 1 was used in Example 6-57, the test piece of lignocellulosic nanofiber dispersion 2 was used in Examples 6-58, and the test piece of cellulose nanofiber dispersion 1 was used in Comparative Examples 6-21, instead of cellulose nanofibers. What was produced in the same manner using glass fiber for Comparative Example 6-22. The filling ratio of the cellulose fibers of Example 6-57, Example 6-58, Comparative Example 6-21, and Comparative Example 6-22 was 30% by mass. In addition, in Examples 6-57 and 6-58, 1 part by mass of an acrylic copolymer compound (BYK-361N, manufactured by Big Chem Japan Co., Ltd.) was added.

As the withstand voltage test, a DC voltage was applied to each of the six test pieces at a boosting speed of 500 V per second, and the voltage to be destroyed was measured. A case in which the average of 6 sheets was 6.5 kV or more was evaluated as ○, and a case where the average of 6 sheets was less than 6.5 kV was evaluated as x. As for the result, all of Examples 6-57 and 6-58 were ○, and all of Comparative Examples 6-21 and 6-22 were ×.

In addition, as an insulation reliability test, a DC voltage of 50 V was applied to each of six test pieces, and a stand-alone test was performed in an atmosphere of 130°C and 85% RH, and the time until short-circuit was measured. A case in which the average of 6 sheets was 500 hours or more was evaluated as ○, and a case in which it was less than 500 hours was evaluated as x. As for the result, all of Examples 6-57 and 6-58 were ○, and all of Comparative Examples 6-21 and 6-22 were ×.

100 parts by mass of Soxir SOXR-OB manufactured by Nippon Kodoshi Kogyo Co., Ltd., and 70 parts by mass of methyl ethyl ketone were blended and stirred to obtain a resin solution. This was impregnated into each cellulose nanofiber sheet, left to stand in an atmosphere at 50°C for 12 hours, then taken out and dried at 80°C for 5 hours to prepare a prepreg. Ten sheets of this prepreg were stacked, and 18 µm copper foil was further stacked on the front and the back, and cured with a vacuum press at a temperature of 160°C and a pressure of 2 MPa for 3 hours. Thereafter, a test piece having a pattern of comb-shaped electrodes of IPC standard B pattern was produced by an etching method. The test piece of lignocellulosic nanofiber dispersion 1 was used in Examples 6-59, the test piece of lignocellulosic nanofiber dispersion 2 was used in Examples 6-60, and the test piece of cellulose nanofiber dispersion 1 was used in Comparative Examples 6-23, instead of cellulose nanofibers. What was produced similarly using glass fiber was set as Comparative Example 6-24. The filling ratio of the cellulose fibers of Example 6-59, Example 6-60, Comparative Example 6-23, and Comparative Example 6-24 was 30% by mass. In addition, in Examples 6-59 and 6-60, 1 part by mass of an acrylic copolymer compound (BYK-361N manufactured by BIC Chem Japan Co., Ltd.) was added.

As the withstand voltage test, a DC voltage was applied to each of the six test pieces at a boosting speed of 500 V per second, and the voltage to be destroyed was measured. A case in which the average of 6 sheets was 6 kV or more was evaluated as ○, and a case where the average of 6 sheets was less than 6 kV was evaluated as x. As for the result, all of Examples 6-59 and 6-60 were ○, and all of Comparative Examples 6-23 and 6-24 were ×.

In addition, as an insulation reliability test, a DC voltage of 50 V was applied to each of six test pieces, and a stand-alone test was performed in an atmosphere of 130°C and 85% RH, and the time until short-circuit was measured. A case in which the average of 6 sheets was 400 hours or more was evaluated as ○, and a case in which it was less than 400 hours was evaluated as x. As for the result, all of Examples 6-59 and 6-60 were ○, and all of Comparative Examples 6-23 and 6-24 were ×.

Examples 6-13 to 6-24 and Comparative Examples 6-5 to 6-8 were superimposed on the front and back of a 0.5 mm-thick sheet of 18 µm copper foil, and a vacuum press at a temperature of 190°C and a pressure of 0.5 MPa It was heated for 1 minute under the conditions of. Thereafter, a test piece having a pattern of comb-shaped electrodes of IPC standard B pattern was produced by an etching method.

As the withstand voltage test, a DC voltage was applied to each of the six test pieces at a boosting speed of 500 V per second, and the voltage to be destroyed was measured. A case in which the average of 6 sheets was 4.5 kV or more was evaluated as ○, and a case in which it was less than 4.5 kV was evaluated as x. As for the result, all of Examples 6-13 to 6-24 were ○, and all of Comparative Examples 6-5 to 6-8 were ×.

In addition, as an insulation reliability test, a DC voltage of 50 V was applied to each of six test pieces, and a stand-alone test was performed in an atmosphere of 130°C and 85% RH, and the time until short-circuit was measured. A case in which the average of 6 sheets was 400 hours or more was evaluated as ○, and a case in which it was less than 400 hours was evaluated as x. As for the result, all of Examples 6-13 to 6-24 were ○, and all of Comparative Examples 6-5 to 6-8 were ×.

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

1, 3, 8, 11: conductor pattern
2: core substrate
1a, 4: connection part
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 via
16: plating layer
17: etching resist pattern
18: wiring pattern
21: Copper clad laminate (test board)
21a: conductor layer
21b: insulating layer
22: insulating resin layer
23: laser via
24: plating layer
25: etching resist pattern
26: wiring pattern
27: through hole
28: through hole

Claims (11)

A binder component that is a thermoplastic resin or a thermosetting resin,
Cellulose nanofibers having a number average fiber diameter of 3 nm to 1000 nm,
A printed wiring board material containing 0.01 to 3 parts by mass of an acrylic copolymer compound in an amount of 0.01 to 3 parts by mass relative to 100 parts by mass of the binder component,
The thermoplastic resin is at least any one of polyethylene, polypropylene and polyamideimide,
The printed wiring board material, wherein the thermosetting resin is any one of an epoxy resin and a thermosetting polyimide. 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 thermosetting resin. The printed wiring board material according to claim 1, comprising a layered silicate. The printed wiring board material according to claim 1, comprising one or both of a silicone compound and a fluorine compound. The printed wiring board material according to claim 1, further comprising cellulose fibers having a number average fiber diameter of 3 nm or more and less than 1000 nm, and a number average fiber diameter of 1 µm or more. The printed wiring board material according to claim 1, wherein the cellulose nanofiber has a carboxylate salt in its structure. The printed wiring board material according to claim 1, wherein the cellulose nanofibers are made from lignocellulose. The printed wiring board material according to claim 1, which is for a solder resist. The printed wiring board material according to claim 1, which is 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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