TWI637991B - Solder resist composition and printed wiring board using the same - Google Patents

Abstract

The present invention provides a solder resist composition which has good insulating properties and can suppress cracking during solder heat resistance, and further has a coating property which can follow the shape of the formed circuit, and provides for use. A printed wiring board of the solder resist composition.

The solder resist composition of the present invention comprises a curable resin and cellulose nanofibers having a number average fiber diameter of 3 nm to 1000 nm. The printed wiring board of the present invention has a cured product obtained by using the solder resist composition.

Description

Solder resist composition and printed wiring board using the same

The present invention relates to a solder resist composition and a printed wiring board using the same.

The printed wiring board is formed on a substrate to form a conductor pattern, and the electronic component is mounted on a land of the conductor circuit by soldering, and a circuit portion other than the land is covered with a solder resist film for protecting the conductor. Such a solder resist film has a function of preventing solder from adhering to an unnecessary portion and preventing oxidation or corrosion of the circuit while mounting the electronic component on the printed wiring board.

Therefore, in addition to various properties such as insulation properties and solder heat resistance, the material for forming the solder resist film is required to have a shape that satisfactorily follows the formed circuit, and the circuit has excellent coating properties.

As a conventional technique related to a solder resist material, for example, Patent Document 1 discloses a photosensitive resin composition containing (A) a polymer having a carboxyl group and (B) a photopolymerizable compound having an ethylenically unsaturated bond, (C) Photopolymerization initiator, and (D) microcapsules containing epoxy resin, but with the improvement of the performance requirements for printed wiring boards, it is required to achieve More excellent solder resist.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Laid-Open Patent Publication No. 2010-128317 (Patent Patent Application, etc.)

A first object of the present invention is to provide a solder resist composition which has good insulating properties and can suppress cracking during solder heat resistance, and further has good coating properties which can follow the shape of the formed circuit, and provides for use. A printed wiring board of the solder resist composition.

Further, a second object of the present invention is to provide a printed wiring board material which can realize a lower coefficient of linear expansion than in the past, and a printed wiring board using the same.

Further, a third object of the present invention is to provide a printed wiring board material capable of suppressing occurrence of migration between holes, and to provide a printed wiring board using the material.

Still further, a fourth object of the present invention is to provide a printed wiring board material which can achieve higher peel strength than in the past, and a printed wiring board using the same.

Further, a fifth object of the present invention is to provide a printed wiring board material excellent in crack resistance and to provide printed wiring using the material. board.

Still further, a sixth object of the present invention is to provide a printed wiring board material which is used in a high-definition circuit or a high-current application, has high withstand voltage between circuits, and can maintain high insulation reliability over a long period of time, and provides A printed wiring board using this material.

As a result of intensive research, the inventors of the present invention have found that by using a solder resist composition containing cellulose nanofibers having a specified fiber diameter, the first object of the invention can be achieved, and the present invention is completed. .

That is, the solder resist composition of the present invention is characterized by comprising a curable resin and cellulose nanofibers having a number average fiber diameter of 3 nm to 1000 nm.

In the solder resist composition of the present invention, those selected from the group consisting of a thermosetting resin and a photocurable resin can be suitably used as the curable resin. Further, in the solder resist composition of the present invention, a resin containing a carboxyl group is preferably used as the curable resin.

The solder resist composition of the present invention preferably comprises a layered niobate. Moreover, it is preferable that the solder resist composition of the present invention contains either or both of a polyoxonium compound and a fluorine compound. Further, in the solder resist composition of the present invention, it is preferable that the cellulose nanofiber has a number average fiber diameter of 3 nm or more and less than 1000 nm, and further includes a cellulose fiber having a number average fiber diameter of 1 μm or more.

Further, in the solder resist composition of the present invention, the cellulose nanofiber preferably has a carboxylate in its structure. Further, in the solder resist composition of the present invention, the cellulose nanofiber is preferably made of lignocellulose.

Further, the dry film of the present invention is characterized in that the above-described solder resist composition of the present invention is applied and dried on a carrier film.

Further, the cured product of the present invention is characterized in that the above-described solder resist composition of the present invention is coated and dried on a substrate to obtain a dried coating film, or the solder resist composition is applied and dried on a carrier film to obtain a dry film. The film is obtained by laminating the dry film on a substrate to form a coating film, and curing the coating film.

Further, the printed wiring board of the present invention is characterized by having the above-described cured product of the present invention.

As a result of intensive research, the inventors of the present invention have found that by combining cellulose nanofibers with layered niobate and blending them into printed wiring board materials, even in the case of blending only one of them, even a small amount The blending amount can also greatly reduce the coefficient of linear expansion, and can achieve the second object of the invention, 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, a cellulose nanofiber having a number average fiber diameter of 3 nm to 1000 nm, and a layered niobate.

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

Moreover, the printed wiring board of the present invention is characterized in that the above-described printed wiring board material of the present invention is used.

As a result of intensive studies, the inventors of the present invention have found that it is possible to achieve the third object of the invention by using either or both of a polyoxonium compound and a fluorine compound as a printed wiring board material.

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 from 3 nm to 1000 nm, and either or both of a polyoxonium compound and a fluorine compound.

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

Moreover, the printed wiring board of the present invention is characterized in that the above-described printed wiring board material of the present invention is used.

As a result of intensive research, the team of the present invention found that by combining cellulose fibers having different fiber diameters and blending the same into the printed wiring board material, the peel strength can be improved, and the fourth object of the invention can be achieved. 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 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.

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

Moreover, the printed wiring board of the present invention is characterized in that the above-described printed wiring board material of the present invention is used.

As a result of intensive studies, the inventors of the present invention have found that the present invention can be accomplished by using a specific cellulose nanofiber as a printed wiring board material up to the fifth object of the invention.

That is, the printed wiring board material of the present invention is characterized by comprising a binder component and a cellulose nanofiber having a number average fiber diameter of 3 nm to 1000 nm having a carboxylate in the structure.

In the present invention, it is preferred that the cellulose nanofiber is a natural cellulose fiber as a raw material, and the natural cellulose fiber is used as an oxidation catalyst in an aqueous solution of an N-oxyl compound. The oxidation is carried out by causing the co-oxidant to act. Further, in the printed wiring board material of the present invention, a thermoplastic resin and a curable resin can be suitably used as the binder component. The printed wiring board material of the present invention can be suitably used for an interlayer insulating material for a solder resist, a core material, and a multilayer printed wiring board.

Moreover, the printed wiring board of the present invention is characterized in that the above-described printed wiring board material of the present invention is used.

The inventors of the present invention have found through intensive research that by using a specific cellulose nanofiber as a printed wiring board material, The sixth object of the invention is to complete the invention.

That is, the printed wiring board material of the present invention is characterized by comprising a cellulose nanofiber having a number average fiber diameter of 3 nm to 1000 nm and a binder component produced from lignocellulose.

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

Moreover, the printed wiring board of the present invention is characterized in that the above-described printed wiring board material of the present invention is used.

According to the present invention, by providing a curable resin and a cellulose nanofiber having a number average fiber diameter of 3 nm to 1000 nm, it is possible to have good insulating properties and suppress cracking during solder heat resistance, and furthermore A coated solder resist composition that closely follows the shape of the formed circuit, and a printed wiring board using the solder resist composition.

Further, according to the present invention, by combining the cellulose nanofibers with the layered niobate, it is possible to realize a printed wiring board material having a lower coefficient of linear expansion than the conventional one, and to realize the use of the printed wiring board. Printed wiring board for materials.

Further, according to the present invention, by providing either or both of a polyoxosiloxane compound and a fluorine compound, it is possible to realize a printed wiring board material capable of suppressing occurrence of migration between holes, and using the same. Printed wiring board for printed wiring board materials.

Further, according to the present invention, by making the cellulose fibers having different composite fiber diameters and blending them, it is possible to realize a printed wiring board material having higher peel strength than in the related art, and printing using the printed wiring board material can be realized. Wiring board.

Further, according to the present invention, a printed wiring board material excellent in crack resistance and a printed wiring board using the printed wiring board material can be obtained by forming a cellulose nanofiber having a carboxylate in the structure.

Further, according to the present invention, by using cellulose nanofibers produced from lignocellulose, high-voltage circuits or high-current applications can achieve high withstand voltage between circuits and can maintain a long period of time. A printed wiring board material having high insulation reliability and a printed wiring board using the printed wiring board material.

1, 3, 8, 11‧‧‧ conductor pattern

2‧‧‧ core substrate

1a, 4‧‧‧ joints

5‧‧‧through hole

6, 9‧‧‧ interlayer insulation

7, 10‧‧‧ vias

12‧‧‧Anti-flux layer

21‧‧‧Copper laminates (test substrate)

21a‧‧‧Conductor layer

21b‧‧‧Insulation

22‧‧‧Insulating resin layer

23‧‧‧Laser vias

24‧‧‧ plating layer

25‧‧‧ Etched photoresist pattern

26‧‧‧Wiring pattern

27‧‧‧through holes

28‧‧‧through hole

Fig. 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 view showing a method of producing an evaluation substrate for an interlayer insulating material in an embodiment.

Fig. 3 is an explanatory view showing a method of producing a substrate for evaluation of a core material in the embodiment.

[Fig. 4] Production of a substrate for evaluation of other core materials in the examples An illustration of the method.

[Best Mode for Carrying Out the Invention]

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

[First aspect of the invention]

The solder resist composition of the present invention is characterized by comprising a curable resin and a cellulose nanofiber having a number average fiber diameter of 3 nm to 1000 nm. Such a cellulose nanofiber can be obtained as follows.

(Cellulose nanofibers with a mean fiber diameter of 3 nm to 1000 nm)

As a raw material of the cellulose nanofiber, pulp, enamel or celorofan obtained from natural plant fiber raw materials such as wood or hemp, bamboo, cotton, jute, kenaf, sugar beet, agricultural waste, and cloth can be used. Among the regenerated cellulose fibers such as cellophane), pulp is particularly suitable. As the pulp, chemical pulp, semi-chemical pulp, chemical pulp, chemical mechanical pulp such as kraft pulp or sulfite pulp obtained by pulping a plant material by chemical or mechanical properties or both may be used. , hot-milled mechanical pulp, chemical hot-milled mechanical pulp, finely ground wood pulp, ground wood pulp, and deinked waste pulp, magazine waste paper pulp, carton waste paper pulp, etc., which are mainly composed of such plant fibers. Among them, various kraft pulps derived from conifers with strong fiber strength, for example, conifer unbleached kraft pulp, conifer oxygen exposure Unbleached kraft pulp and conifer bleached kraft pulp are suitable.

The above-mentioned raw materials are mainly composed of cellulose, hemicellulose, and lignin. Among them, the content of lignin is usually about 0 to 40% by mass, and particularly about 0 to 10% by mass. For these raw materials, the lignin removal can be carried out to the bleaching treatment as needed to adjust the amount of lignin. Still, the measurement of the lignin content can be carried out by the Klason method.

Among the cell walls of plants, cellulose molecules are not monomolar, but regularly aggregate and form crystalline microfibers (cellulose nanofibers) having dozens of aggregates, which becomes the basic skeleton material of plants. Therefore, in order to produce cellulose nanofibers from the above-mentioned raw materials, the fibers can be loosened to the naphthalene by applying a pulverization treatment to the above-mentioned raw materials, a high-temperature high-pressure steam treatment, a treatment with phosphate, or the like. The method of rice size.

Among the above, the method of knocking the pulverization treatment to apply a direct strength to the raw material such as the pulp to mechanically knock to pulverize and loosen the fiber to obtain the cellulose nanofiber. More specifically, for example, pulp or the like is mechanically treated by a high-pressure homogenizer or the like to form an aqueous suspension, wherein about 0.1 to 3% by mass of the aqueous suspension is cellulose which is loose to a fiber diameter of about 0.1 to 10 μm. Further, the fiber suspension is repeatedly ground to a pulverization treatment by a grinder or the like to obtain a cellulose nanofiber having a fiber diameter of about 10 to 100 nm.

The above-mentioned grinding to the pulverization treatment can be carried out, for example, by using a grinder "Pure Fine Mill" manufactured by Kurita Machinery Co., Ltd. or the like. This grinding When the raw material is passed through the gap between the upper and lower grinding machines, the raw material is pulverized to the ultrafine particles by the crushing, centrifugal force and shearing force generated, and the cutting can be simultaneously performed. Grinding, micronizing, dispersing, emulsifying and fibrillating. Further, the above-mentioned grinding to the pulverization treatment can also be carried out by using a superfine-grinding machine "Super Mass-colloider" manufactured by Zengxing Industry Co., Ltd. The ultra-colloidal machine is beyond the scope of pure pulverization, and it is possible to achieve an ultrafine-grained pulverizer such as a degree of melting. The super colloidal machine is a superfine particle grinding machine in the form of a stone crucible composed of two non-porous whetstones which can be freely adjusted. The upper end grinding blade is fixed, and the lower end grinding stone is high speed rotation. The raw materials put into the hopper are sent to the gap between the upper and lower whetstones by centrifugal force, and the raw materials are sequentially ground and superfinely formed by the strong compression, shearing, and rolling friction generated by the space.

Further, the high-temperature high-pressure steam treatment is a method of obtaining cellulose nanofibers by exposing the raw material such as the pulp to high-temperature high-pressure steam to loosen the fibers.

Further, the above treatment with phosphate or the like is carried out by phosphating the surface of the raw material such as the pulp to weaken the binding force between the cellulose fibers, followed by fine grinding (grinding to crushing) Treatment) The fibers are loosened to obtain a cellulose treatment. For example, the raw material such as the pulp is immersed in a solution containing 50% by mass of urea and 32% by mass of phosphoric acid, and the solution is sufficiently infiltrated between the cellulose fibers at 60° C., and then heated at 180° C. to carry out phosphorylation. After washing with water, it was hydrolyzed in a 3 mass% hydrochloric acid aqueous solution at 60 ° C for 2 hours, and again After washing with water, the mixture is treated in a 3% by mass aqueous sodium carbonate solution at room temperature for about 20 minutes to complete phosphorylation, and the treated product is defibrated by fine grinding (the above-mentioned attritor or the like) to obtain cellulose. fiber.

Further, the cellulose nanofiber used in the present invention may be chemically modified and/or physically modified to improve the functionality. Here, as a chemical modification, a functional group may be added by acetalization, acetonitrile, cyanoethylation, etherification, isocyanation or the like, or an inorganic substance such as phthalate or titanate may be chemically used. It is carried out by a method such as a reaction or a gel method or the like, which is compounded or coated. As a method of chemical modification, the method of immersing in the acetic acid anhydride of the formed flaky cellulose nanofibers, and heating, for example is mentioned. Further, examples of the physical modification include physical vapor deposition (PVD), chemical vapor deposition (CVD), electroless plating, or electrolytic plating by vacuum deposition, ion deposition, and sputtering. A method of coating a metal or ceramic material by a plating method or the like. These modifications may be before or after the above treatment.

The number average fiber diameter of the cellulose nanofiber used in the present invention must 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 cellulose nanofiber single fiber is 3 nm, it is substantially impossible to manufacture less than 3 nm, and when it exceeds 1000 nm, in order to obtain the desired effect of the present invention, it is necessary to add an excessive amount to deteriorate the film forming property. . In addition, the average fiber diameter of the cellulose nanofibers is observed by a SEM (Scanning Electron Microscope) or a TEM (Transmission Electron Microscope), and is pulled out diagonally on the photograph. Straight line, random After the 12 points of the fiber near the line were extracted, the thickest fiber and the finest fiber were removed, and the remaining 10 points were measured, and the average value was taken.

The blending amount of the cellulose nanofibers used in the present invention is preferably 0.1 to 80% by mass, and more preferably 0.2 to 70% by mass based on the total amount of the composition after solvent removal. When the blending amount of the cellulose nanofibers is 0.1% by mass or more, the desired effects of the present invention can be favorably obtained. On the other hand, when it is 80% by mass or less, film formability can be improved.

Further, in the present invention, a method in which the cellulose nanofibers are formed into a sheet shape, and the binder component is impregnated into the flaky cellulose nanofibers and dried to prepare a prepreg may be used. The content of the cellulose nanofiber in the prepreg is the same as the amount of the cellulose nanofiber blended.

(curable resin)

The curable resin used in the present invention is preferably a resin selected from the group consisting of a thermosetting resin and a photocurable resin, and may be a mixture thereof.

In addition, as the thermosetting resin, a resin which can be cured by heating and exhibits electrical insulating properties may be used, and examples thereof include an epoxy compound, an oxetane compound, a melamine resin, a polyoxyl resin, and the like. . In the present invention, it is particularly preferred to use an epoxy compound and/or an oxetane compound.

As the epoxy compound, one or more can be used. Among the known compounds of the epoxy group, among them, a compound having two or more epoxy groups is preferred. For example, a monoepoxy compound such as a butyl glycidyl ether, a phenyl glycidyl ether or a monoepoxy compound such as glycidyl (meth)acrylate, a bisphenol A epoxy resin, or a bisphenol S ring may be mentioned. Oxygen resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, cresol novolac type epoxy resin, alicyclic 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, A compound having two or more epoxy groups in one molecule such as (2,3-epoxypropyl)isocyanurate or triglycidyl ginate (2-hydroxyethyl)isocyanurate. These compounds may be used alone or in combination of two or more depending on the desired properties. Examples of the epoxy compound include, for example, ADK-CIZER O-130P, O-180A, D-32, D-55, manufactured by ADEKA, 604, 807, 828, 834, and 1001 manufactured by Mitsubishi Chemical Corporation. 1004, YL903, 152, 154, 157S, YL-6056, YX-4000, YL-6121, (share) DAICEL CELOXIDE 2021, EHPE3150, PB-3600, DIC (share) EPICLON 830, 840, 850, 1050, 2055, 152, 165, N-730, N-770, N-865, EXA-1514, HP-4032, EXA-4750, EXA-4700, HP-7200, HP-7200H, Nippon Steel & Sumitomo Chemical Co., Ltd. EPOTOHTO YDF-170, YDF-175, YDF-2004, EPOTOHTO YD-011, YD-013, YD-127, YD-128, EPOTOHTO YDC-1312, EPOTOHTO YSLV-80XY, YSLV-120TE, EPOTOHTO YDB -400, YDB-500, EPOTOHTO YDCN- 701, YDCN-704, EPOTOHTO YR-102, YR-450, EPOTOHTO ST-2004, ST-2007, ST-3000, ZX-1063, ESN-190, ESN-360, DOW CHEMICAL Japan (stock) DER317 331, 661, 664, 664, 542, DEN431, 438, TEN, EPPN-501, EPPN-502, Sumitomo Chemical Co., Ltd. SUMIEPOXY ESA-011, ESA-014, ELA-115, ELA-128, ESB- 400, ESB-700, ESCN-195X, ESCN-220, ELM-120, Asahi Kasei E-MATERIALS (shares) AER330, 331, 661, 664, 711, 714, ECN-235, ECN-299, Nipponization EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, NC-3000, NC-3100, manufactured by Nissan Chemical Industries Co., Ltd., manufactured by Nissan Chemical Industries Co., Ltd. BLEMMER DGT, CP-50S, CP-50M, etc., but are not limited to these. These epoxy resins may be used alone or in combination of two or more.

Next, an oxetane compound will be described.

Specific examples of the oxetane compound containing the oxetane ring represented by the following general formula (I),

(In the formula, R ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), for example, 3-ethyl-3-hydroxymethyloxetane (manufactured by Toago Corporation), trade name OXT- 101), 3-ethyl-3-(phenoxymethyl)oxetane (manufactured by Toagosei Co., Ltd., trade name OXT-211), 3-ethyl-3-(2-ethylhexyl) Oxymethyl)oxetane (manufactured by Toagosei Co., Ltd., trade name OXT-212), 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy] Methyl}benzene (manufactured by East Asia Synthetic Co., Ltd., trade name: OXT-121), bis(3-ethyl-3-oxetanylmethyl)ether (manufactured by East Asia Synthetic Co., Ltd., trade name: OXT-221) . Further, a phenol novolac type oxetane compound or the like can be given. These oxetane compounds may be used in combination with the above epoxy compounds, or may be used singly.

Next, the photocurable resin may be a resin which can be cured by irradiation with an active energy ray and exhibits electrical insulating properties. In the present invention, a compound having one or more ethylenically unsaturated bonds in the molecule is specifically used. Preferably.

As the compound having an ethylenically unsaturated bond, a known photopolymerizable oligomer, a photopolymerizable vinyl monomer, or the like can be used. In the above, examples of the photopolymerizable oligomer include an unsaturated polyester oligomer and a (meth)acrylate oligomer. Examples of the (meth) acrylate-based oligomer include phenol novolac epoxy (meth) acrylate, cresol novolac epoxy (meth) acrylate, and bisphenol epoxy (meth) acrylate. Epoxy (meth) acrylate, urethane (meth) acrylate, epoxy urethane (meth) acrylate, polyester (meth) acrylate, polyether (methyl) Acrylate, polybutadiene modified (meth) acrylate, and the like. Further, in the present specification, the term "(meth)acrylate" refers to the term "acrylate", methacrylate, and the like, and the other similar expressions are also the same.

As the photopolymerizable vinyl monomer, a known one may be used, and examples thereof include a styrene derivative such as styrene, chlorostyrene or α-methylstyrene; vinyl acetate, vinyl butyrate or benzoic acid; Vinyl esters such as vinyl ester; vinyl isobutyl ether, vinyl-n-butyl ether, vinyl-t-butyl ether, vinyl-n-pentyl ether, vinyl isoamyl ether, ethylene Vinyl ethers such as benzyl-n-octadecyl ether, vinyl cyclohexyl ether, ethylene glycol monobutyl vinyl ether, triethylene glycol monomethyl vinyl ether; acrylamide, methacryl Indoleamine, N-hydroxymethylpropenylamine, N-hydroxymethylmethacrylamide, N-methoxymethylpropenylamine, N-ethoxymethylpropenamide, N-butoxy (meth) acrylamide such as methacrylamide; allyl compound such as triallyl isocyanurate, diallyl phthalate or diallyl isophthalate 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, phenyl (meth)acrylate, (A) Base) An ester of (meth)acrylic acid such as acid phenoxyethyl ester; a hydroxyalkane such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate or neopentaerythritol tri(meth)acrylate Alkoxyalkylene glycol mono(meth)acrylates such as methoxy(meth)acrylate; methoxyethyl (meth)acrylate; ethoxyethyl (meth)acrylate; Alcohol di(meth)acrylate, butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, trihydroxyl a alkylene polyol poly(meth)acrylate such as methyl propane tri(meth)acrylate, neopentyltetrakis(meth)acrylate or dipentaerythritol hexa(meth)acrylate; Diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, ethoxylated trimethylol Polyoxyalkylene glycol poly(meth)acrylates such as propane triacrylate, propoxylated trimethylolpropane tri(meth)acrylate; hydroxytrimethylacetate neopentyl glycol ester Poly(meth)acrylates such as (meth)acrylate; isomeric isocyanate poly(meth)acrylates such as [(meth)acryloxyethyl]isocyanurate Classes, etc. These may be used alone or in combination of two or more depending on the required characteristics.

(resin containing carboxyl group)

Moreover, when the solder resist composition of the present invention is an alkali-developing photosensitive resin composition, it is preferred to contain a resin containing a carboxyl group. The carboxyl group-containing resin may be a carboxyl group-containing photosensitive resin having an ethylenically unsaturated group.

As the resin containing a carboxyl group, a resin (either an oligomer or a polymer) exemplified 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 which is modified to adjust a molecular weight or an acid value.

(2) A carboxyl group-containing (meth)acrylic copolymer resin is reacted with a compound having an oxirane ring and an ethylenically unsaturated group in one molecule to obtain a photosensitive carboxyl group-containing resin.

(3) reacting an unsaturated carboxylic acid with a copolymer, wherein the copolymer is a copolymer of a compound having one epoxy group and an unsaturated double bond in one molecule and a compound having an unsaturated double bond, and then The second-order hydroxyl group formed by the reaction is reacted with a saturated or unsaturated polybasic acid anhydride to obtain a photosensitive carboxyl group-containing resin.

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

(5) A polyfunctional epoxy compound is reacted with an unsaturated monocarboxylic acid, and a part or all of the secondary hydroxyl group formed by the reaction is reacted with a polybasic acid anhydride to obtain a photosensitive carboxyl group-containing resin.

(6) "Polyfunctional epoxy compound", "a compound having two or more reactive groups other than a hydroxyl group and a hydroxyl group reactive with an epoxy group in one molecule", and "an unsaturated group-containing monocarboxylic acid" The reaction is carried out, and the obtained reaction product is further reacted with a polybasic acid anhydride to obtain a carboxyl group-containing photosensitive resin.

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

(8) reacting a "polyfunctional epoxy compound", "a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule" with a "monocarboxylic acid containing an unsaturated group", and obtaining the obtained The alcoholic hydroxyl group of the reaction product is reacted with an acid anhydride group of a polybasic acid anhydride to obtain a carboxyl group-containing photosensitive resin.

Among these, in the photosensitive carboxyl group-containing resin of the above (2), (a) a carboxyl group-containing (meth)acrylic copolymer resin and (b) one molecule having an oxirane ring and A copolymerized resin having a carboxyl group obtained by a reaction of a compound having an ethylenically unsaturated group is preferred.

(a) a carboxyl group-containing (meth)acrylic copolymer resin which has "unsaturated group" in "(meth)acrylate" and "one molecule" A compound of at least one carboxyl group is obtained by copolymerization. Examples of the (meth) acrylate constituting the copolymer resin (a) include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and butyl (meth)acrylate. (meth)acrylic acid alkyl esters such as ester, amyl (meth)acrylate, hexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, (A) a carboxyl group-containing (meth) acrylate such as hydroxybutyl acrylate or caprolactone modified 2-hydroxyethyl (meth)acrylate, methoxydiethylene glycol (meth) acrylate, Ethoxydiethylene glycol (meth) acrylate, isooctyloxy diethylene glycol (meth) acrylate, phenoxy triethylene glycol (meth) acrylate, methoxy triethylene glycol A diol-modified (meth) acrylate such as (meth) acrylate or methoxypolyethylene glycol (meth) acrylate. These may be used singly or in combination of two or more.

Further, examples of the compound having one unsaturated group and at least one carboxyl group in one molecule include, for example, acrylic acid, methacrylic acid, and a chain-extended modified unsaturated monocarboxylic acid between an unsaturated group and a carboxylic acid. For example, β-carboxyethyl (meth)acrylate, 2-propenyloxyethyl succinic acid, 2-propenyloxyethylhexahydrophthalic acid, lactone modification, etc., having an ester bond An unsaturated monocarboxylic acid, a modified unsaturated monocarboxylic acid having an ether bond, and a carboxyl group having two or more maleic acids in the molecule. These may be used singly or in combination of two or more.

Examples of the compound having an oxirane ring and an ethylenically unsaturated group in the (b) molecule include, for example, glycidyl (meth)acrylate and α-methylglycidyl (meth)acrylate. 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexyl (meth) acrylate Ester, 3,4-epoxycyclohexyl (meth)acrylate, 3,4-epoxycyclohexylmethyl acrylate, and the like. Among them, 3,4-epoxycyclohexylmethyl (meth)acrylate is preferred. The compound having an oxirane ring and an ethylenically unsaturated group in the above (b) molecule may be used singly or in combination of two or more.

The resin having a carboxyl group preferably has an acid value in the range of 50 to 200 mgKOH/g. When the acid value is less than 50 mgKOH/g, it is difficult to remove the unexposed portion of the coating film of the solder resist composition with a weak alkali aqueous solution. On the other hand, when the acid value exceeds 200 mgKOH/g, there are problems such as water resistance and poor electrical properties of the cured film. Further, the resin having a carboxyl group preferably has a mass average molecular weight of from 5,000 to 100,000. When the mass average molecular weight is less than 5,000, the dryness of the touch of the coating film of the solder resist composition tends to be deteriorated. Further, when the mass average molecular weight exceeds 100,000, the developability and storage stability of the solder resist composition tend to deteriorate.

(photopolymerization initiator)

In the solder resist composition of the present invention, when a photocurable resin is used to the carboxyl group-containing photosensitive resin, it is more preferable to add a photopolymerization initiator. Examples of the photopolymerization initiator include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzyl methyl ketal, and alkyl ethers thereof. Acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, diethoxyacetophenone, 2 ,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio) Phenyl]- Acetophenones such as 2-morpholinyl-propan-1-one; methyl hydrazine, 2-ethyl hydrazine, 2-tert-butyl hydrazine, 1-chloroindole, 2-pentyl hydrazine Anthraquinones such as thioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-methylthiothioxanthone, 2, a thioxanthone such as 4-diisopropylthioxanthone; a ketal such as acetophenone dimethyl ketal or benzyl dimethyl ketal; diphenyl ketone or 4,4-dimethyl A diphenyl ketone or the like such as an aminodiphenyl ketone. These may be used alone or in combination of two or more types, and may be a tertiary amine such as triethanolamine or methyldiethanolamine; 2-dimethylaminoethylbenzoic acid or 4-dimethylaminobenzoic acid A photopolymerization start aid such as a benzoic acid derivative such as an ester is used in combination.

The blending amount of the photopolymerization initiator is preferably a ratio which is usually used, and is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 20 parts by mass, based on 100 parts by mass of the photocurable resin and/or the carboxyl group-containing resin. 1 to 10 parts by mass.

(hardener and hardening catalyst)

Further, in the solder resist composition of the present invention, when a thermosetting resin is used, a curing agent and/or a curing catalyst may be further added.

Examples of the curing agent include polyfunctional phenol compounds, polycarboxylic acids and their anhydrides, aliphatic or aromatic primary or secondary amines, polyamine resins, polyfluorenyl compounds, and the like. Among these, it is preferred to use a polyfunctional phenol compound, a polycarboxylic acid, and an acid anhydride thereof in terms of workability and insulating properties.

As a polyfunctional phenol compound, as long as it has 2 in one molecule A compound having a phenolic hydroxyl group or more may be used, and a known one can be used. Specific examples thereof include phenol novolac resin, cresol novolac resin, bisphenol A, allylated bisphenol A, bisphenol F, phenolic resin of bisphenol A, and vinylphenol copolymerization. A resin or the like is particularly preferably a phenol novolac resin in that the effect of high reactivity and heat resistance is high. Such a polyfunctional phenol compound may be subjected to an addition reaction with an epoxy compound and/or an oxetane compound in the presence of a suitable hardening catalyst.

The polycarboxylic acid and its acid anhydride are compounds having two or more carboxyl groups in one molecule and an acid anhydride thereof, and examples thereof include a copolymer of (meth)acrylic acid, a copolymer of maleic anhydride, and a condensate of a diprotonic acid. For the commercial product, for example, JONCRYL (commodity group name) manufactured by BASF Corporation, SMA RESIN (commodity group name) manufactured by SARTOMER Co., Ltd., and polysebacic anhydride manufactured by Shin-Nippon Chemical Co., Ltd., and the like.

The blending amount of the hardening agent is preferably a ratio which is usually used, and is preferably from 1 to 200 parts by mass, more preferably from 10 to 100 parts by mass, per 100 parts by mass of the thermosetting resin.

Next, the curing catalyst can be used as a curing catalyst compound in the reaction of an epoxy compound and/or an oxetane compound with the above-mentioned curing agent, or a compound which is a polymerization catalyst when a curing agent is not used. . Specific examples of the curing catalyst include, for example, a tertiary amine, a tertiary amine salt, a quaternary phosphonium salt, a tertiary phosphine, a crown ether complex, and a phosphonium ylide. It can be used alone or in combination of two or more types. Among them, for example, imidazoles such as trade names 2E4MZ, C11Z, C17Z, and 2PZ, or azine compounds of imidazoles such as 2MZ-A and 2E4MZ-A, and 2MZ-OK are commercially available. Imidazole isocyanate of 2PZ-OK or the like, imidazole hydroxymethyl group such as 2PHZ or 2P4MHZ (the above-mentioned trade names are all manufactured by Shikoku Chemical Industries Co., Ltd.), dicyandiamide and its derivatives , melamine and its derivatives, diamine maleic acid and its derivatives, diethylenetriamine, triethylenetetramine, tetraethyleneamine, bis(hexamethylene)triamine, triethanolamine, An amine such as diaminodiphenylmethane or an organic acid, or 1,8-dibicyclo[5,4,0]undecene-7 (trade name: DBU, manufactured by San-Apro Co., Ltd.) ,3,9-bis(3-aminopropyl)-2,4,8,10-four An organic phosphine compound such as spiro[5,5]undecane (trade name ATU, manufactured by Ajinomoto) or triphenylphosphine, tricyclohexylphosphine, tributylphosphine or methyldiphenylphosphine Wait.

The blending amount of the curing catalyst is sufficient in a usual ratio, and is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 3 parts by mass, per 100 parts by mass of the thermosetting resin.

Further, the solder resist composition of the present invention preferably contains a layered niobate. By combining the cellulose nanofibers with the layered niobate and blending them, since the synergistic effect is achieved, the linear expansion coefficient can be greatly reduced even with a small amount of blending. material. Regarding the layered niobate, the following can be used.

Further, the solder resist composition of the present invention preferably contains either or both of a polyoxonium compound and a fluorine compound. The polyoxo compound and the fluorine compound are combined with the cellulose nanofiber to suppress the occurrence of migration between the respective pores. Regarding the polyoxymethylene compound and the fluorine compound, the following can be used.

Further, the solder resist composition of the present invention preferably comprises 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. High peel strength can be achieved by combining 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. The cellulose fiber having a number average fiber diameter of 1 μm or more can be used as follows.

Further, in the solder resist composition of the present invention, the cellulose nanofiber preferably has a carboxylate in its structure. By having a carboxylate, crack resistance can be improved. Regarding the cellulose nanofiber having a carboxylate, the following can be used.

Further, in the solder resist composition of the present invention, the cellulose nanofiber is preferably made of lignocellulose. When cellulose nanofibers are made of lignocellulose, in high-definition circuits or high-current applications, the withstand voltage between circuits is high, and high insulation reliability can be maintained over a long period of time. Regarding the lignocellulosic nanofiber, the following can be used.

(other adjustment points)

For example, examples of the thermosetting component include an episulfide resin, an amine-based resin such as a melamine derivative or a benzoguanamine derivative, a polyisocyanate compound, or a blocked isocyanate compound.

Further, as the coloring agent, a known person who is represented by chromaticity as a coloring pigment or a dye can be used. For example, Pigment Blue 15, 15:1, 15:2, 15:3, 15:415:6, 16, 60, Solvent Blue 35, 63, 68, 70, 83, 87, 94, 97, 122, 136, 67, 70, Pigment G Reen 7, 36, 3, 5, 20, 28, Solvent Yellow 163, Pigment Yellow 24, 108, 193, 147, 199, 202, 110, 109, 13917918593, 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, 194, 224, 254, 255, 264, 270, 272, 220, 144, 166, 214, 220, 221, 242, 168, 177, 216, 122, 202, 206, 207, 209, Solvent Red 135, 179, 149, 150, 52, 207, Pigment Violet 19, 23, 29, 32, 36, 38, 42, Solvent Violet 13, 36, Pigment Brown 23, 25, Pigment Black 1, 7, etc.

Examples of the organic solvent include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; methyl stilbene and ethyl sirolius; Butyl sirolius, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monoethyl ether, etc. Glycol ethers; esters of ethyl acetate, butyl acetate, serosu acetate, diethylene glycol monoethyl ether acetate, and esterified products of the above glycol ethers; ethanol, C Alcohols such as alcohol, ethylene glycol, and propylene glycol; aliphatic hydrocarbons such as octane and decane; petroleum solvents such as petroleum ether, petroleum brain, hydrogenated petroleum brain, and solvent oil.

Further, an additive such as an antifoaming ‧ leveling agent, a thixotropic imparting agent ‧ a tackifier, a coupling agent, a dispersing agent, a flame retardant, etc. may be used as needed.

As defoamer ‧ leveling agent, polyfluorene oxide, modified polyfluorene oxide, mineral oil, vegetable oil, aliphatic alcohol, fatty acid, metal soap, fatty acid decylamine, polyoxyalkylene glycol A compound such as a polyoxyalkylene alkyl ether or a polyoxyalkylene fatty acid ester.

As a thixotropic imparting agent ‧ tackifier, clay minerals or micro-fine vermiculite, vermiculite gel, amorphous inorganic particles, polyamines such as kaolinite, bentonite, montanite, bentonite, talc, mica, and zeolite can be used. Additives, modified urea-based additives, wax-based additives, and the like.

As the coupling agent, an alkoxy group having a methoxy group, an ethoxy group, an ethenyl group, or the like, having a vinyl group, a methacrylic group, or an acrylic acid can be used. As the reactive functional group, for example, vinyl ethoxy decane, vinyl trimethyl, etc., as a reactive functional group, an epoxy group, a cyclic epoxy group, a decyl group, an amine group, a diamine group, an acid anhydride, a urea group, a thioether group, an isocyanate group or the like. Oxydecane, vinyl. a vinyl decane compound such as β-methoxyethoxy)decane or γ-methacryloxypropyltrimethoxydecane, γ-aminopropyltrimethoxydecane, N-β-( Aminoethyl)γ-aminopropyltrimethoxydecane, N-β-(aminoethyl)γ-aminopropylmethyldimethoxydecane, γ-ureidopropyltriethoxy Amino decane compound such as decane, γ-glycidoxypropyltrimethoxydecane, β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, γ-glycidoxypropyl An epoxy decane compound such as methyl diethoxy decane, an oxime decane compound such as γ-mercaptopropyltrimethoxy decane, or a phenyl group such as N-phenyl-γ-aminopropyltrimethoxydecane. a decane coupling agent such as an amine decane compound, isopropyl triisostearate sulphate, tetraoctyl bis(di-tridecanephosphonium oxy) titanate, bis(dioctyl 焦Phosphonium oxy)oxyacetate titanate, isopropyl trilauryl benzene sulfonate titanate, isopropyl ginseng (dioctyl pyrophosphonium oxy) titanate, tetraisopropyl bis ( Dioctyl phosphite) titanate, tetrakis(1,1-diallyloxy Di-1-(butyl)bis-(di(tridecyl))phosphite titanate, bis(dioctylpyridiniumoxy)-extended ethyl titanate, isopropyltrioctylphosphonic acid Ester, isopropyl dimethyl propylene isostearyl decyl titanate, isopropyl tristearate diacrylate titanate, isopropyl tris(dioctyl phosphate) titanate, isopropyl A titanate coupling agent such as tricumylphenyl titanate, dicumylphenyloxyacetic acid titanate or diisostearate extended ethyl titanate, containing ethylenically unsaturated zirconate a compound, a compound containing a neoalkoxy zirconate, a neoalkoxy neodecyl zirconate, Neoalkoxy (lauryl) benzenesulfonyl zirconate, neoalkoxy (dioctyl) phosphate zirconate, neoalkoxy (dioctyl) pyrophosphate zirconate, Neoalkoxy(ethylenediamine)ethylzirconate, neoalkoxy(m-amino)phenylzirconate, tetrakis(2,2-diallyloxymethyl) Butyl, bis(ditridecyl)phosphite zirconate, neopentyl (diallyl)oxy, trinonyl zirconate, neopentyl (diallyl) Oxylate, tris(lauryl)benzene-sulfonyl zirconate, neopentyl (diallyl)oxy, tris(dioctyl)phosphate zirconate, neopentyl (diallyl) Oxylate, tris(dioctyl)pyrophosphate zirconate, neopentyl (diallyl)oxy, tris(N-extended ethyldiamine)ethylzirconate, neopentyl (II) Allyl)oxy, tris(m-amino)phenylzirconate, neopentyl (diallyl)oxy, trimethylpropenyl zirconate, neopentyl (diallyl) Oxylate, zirconium triacrylate, di-n-pentyl (diallyl)oxy, di-p-aminobenzylbenzyl zirconate, di-n-pentyl (diallyl)oxy, di 3-mercapto)zirconium propionate, zirconium 2,2-bis(2-propionatemethyl)butyrate (I V), ring bis[2,2-(bis 2-propionate methyl)butyrate] pyrophosphate-O, O, etc. zirconate coupling agent, diisobutyl (oleyl) ethyl acetonitrile An aluminate coupling agent such as a mercapto aluminate or an alkylacetate acetate aluminum diisopropyl ester.

As the dispersing agent, a polymer type dispersing agent such as a polycarboxylic acid type, a naphthalenesulfonic acid formalin condensation system, a polyethylene glycol, a polycarboxylic acid partial alkyl ester type, a polyether type, or a polyalkylene polyamine type can be used. A low molecular weight dispersant such as an alkyl sulfonic acid system, a quaternary ammonium compound, a higher alcohol alkylene oxide system, a polyol ester system or an alkyl polyamine system.

As the flame retardant, a hydrated metal system such as aluminum hydroxide or magnesium hydroxide, red phosphorus, ammonium phosphate, ammonium carbonate, zinc borate or stannic acid can be used. Zinc, molybdenum compound, bromine compound, chlorine compound, phosphate, phosphorus-containing polyalcohol, phosphorus-containing amine, melamine cyanurate, melamine compound, triazine compound, hydrazine compound, hydrazine polymer, and the like.

The other synthetic component may, for example, be a photoacid generator such as a photoacid generator such as an azo salt, a phosphonium salt or an iodonium salt, an amine formate compound, an α-aminoketone compound or an O-indenyl ruthenium compound. Polymer, hydroquinone, hydroquinone monomethyl ether, t-butyl catechol, gallic phenol, phenothiazine and other polymerization inhibitors, barium sulfate, globular vermiculite, hydrotalcite and other inorganic fillers, strontium powder, An organic filler such as a nylon powder or a fluorine powder, a radical scavenger, an ultraviolet absorber, an oxidation preventive agent, a peroxide decomposer, an adhesion promoter, a rust preventive agent, and the like.

The solder resist composition of the present invention can be applied and dried on a carrier film (support) to obtain it as a dry film. At the time of dry film formation, the solder resist composition of the present invention is diluted with the above organic solvent and adjusted to a suitable viscosity, and then blade coating, blade coating, lip coating, bar coating, and pressure roller are used. Coating, reverse roll coating, transfer roll coating, gravure coating, spray coating, etc. are applied to the carrier film in a uniform thickness, usually, dried at a temperature of 50 to 130 ° C for 1 to 30 minutes, and Make a dry coating film. The coating film thickness is not particularly limited, and is generally selected from the range of a film thickness after drying of 10 to 150 μm, preferably 20 to 60 μm.

As the carrier film, a plastic film can be used, and a plastic film such as a polyester film such as polyethylene terephthalate, a polyimide film, a polyimide film, a polypropylene film, or a polystyrene film can be used. It is better. The thickness of the carrier film is not particularly limited, and is generally 10 to 150 μm. The scope is to be appropriately selected.

At this time, after the coating film is formed on the carrier film, it is preferable to laminate a peelable cover film on the surface of the coating film for the purpose of preventing dust from adhering to the surface of the coating film or the like. As the peelable cover film, for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a surface-treated paper, or the like can be used, and when the cover film is peeled off, as long as the adhesion between the coating film and the cover film is The adhesion between the coating film and the carrier film is small.

Further, the solder resist composition of the present invention is adjusted to a viscosity suitable for the coating method by using the above organic solvent, and then applied to a substrate by a dip coating method, a flow coating method, a roll coating method, or a rod type. Coating by a coating method, a screen printing method, a curtain coating method, or the like, the organic solvent contained in the composition is volatilized and dried (temporarily dried) at a temperature of about 60 to 100 ° C to form a non-sticky film. (tack free) dry film. Further, the solder resist composition is applied onto a carrier film and dried, and when a dry film is taken as a film, the coating film of the solder resist composition is applied to the substrate by a bonding machine or the like. The contact is applied to the substrate, and then the layer of the coating film can be formed on the substrate by peeling off the carrier film.

These coating films are thermally cured by, for example, irradiation with an active energy ray, or thermally cured by heating to a temperature of from 140 ° C to 180 ° C to obtain a cured product.

The substrate may be, for example, a printed wiring board or a flexible printed wiring board in which a circuit is formed in advance, and examples thereof include paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, and glass cloth. Non-fibrous cloth epoxy, glass cloth/paper epoxy, synthetic fiber epoxy, fluorine, polyethylene A copper-clad laminate of all grades (FR-4, etc.) of materials such as copper-clad laminates for high-frequency circuits such as PPO ‧ cyanate esters, and other polyimide-based films, PET films, glass substrates, and ceramic substrates. Wafer board, etc.

After applying the solder resist composition of the present invention, in order to carry out volatilization drying, a dryer can be used using a hot air circulation type drying oven, an IR furnace, a heating plate, a convection constant temperature oven, or the like using a heat source having a steam heating method using steam. The method of hot air convection contact inside and the method of blowing the support by a nozzle are performed.

The exposure device used for the irradiation of the active energy ray may be a device equipped with a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a mercury short-arc lamp, or the like, and can irradiate ultraviolet rays in the range of 350 to 450 nm. Direct mapping devices (eg, laser direct imaging devices that render images with direct lasers from CAD data from a computer) can be used. As the laser light source of the direct plotter, as long as the laser light having a maximum wavelength of 350 to 410 nm is used, a gas laser or a solid laser can be used. The exposure amount for forming an image differs depending on the film thickness or the like, and is generally set to be in the range of 20 to 800 mJ/cm ² , preferably 20 to 600 mJ/cm ² .

Further, as the developing method, a dipping method, a rinsing method, a spraying method, a brushing method, or the like can be used; as the developing solution, potassium hydroxide, sodium hydroxide, sodium hydrogencarbonate, potassium carbonate, sodium phosphate, or sodium citrate can be used. An aqueous alkali solution such as ammonia or an amine.

The solder resist composition of the present invention has excellent insulating properties, excellent crack resistance when solder is heat resistant, and has good followability Since the shape of the formed circuit is excellent in the coating property, a printed wiring board having excellent insulating properties and heat resistance can be obtained by using a cured product formed of such a solder resist composition.

[Second aspect of the invention]

The printed wiring board material of this embodiment may be a cellulose nanofiber containing a binder component, a number average fiber diameter of 3 nm to 1000 nm, and a layered niobate.

As the cellulose nanofiber, the same state as in the first embodiment can be used.

The blending amount of the cellulose nanofibers in the present embodiment is preferably from 0.04 to 64% by mass, more preferably from 0.08 to 56% by mass, based on the total amount of the composition after solvent removal. When the blending amount of the cellulose nanofibers is 0.04% by mass or more, the effect of lowering the coefficient of linear expansion can be favorably obtained. On the other hand, when it is 64 mass% or less, film formability can be improved.

The layered niobate is not particularly limited, and is preferably a clay mineral or hydrotalcite compound having swelling property and/or cleavability, and the like. Examples of such clay minerals include kaolinite, dickite, pearl kaolinite, halloysite, serpentine, serpentine, pyrophyllite, Montestone, Bedstone, iron bentonite, and saponite. , saponite, saponin, lithium bentonite, tetrasilicic mica, sodium taeniolite, muscovite, pearl mica, talc, vermiculite, phlogopite, green crisp mica, green mud Stone and so on. The layered citrate can be It is a natural substance or a synthetic substance. Further, the layered citrate may be used singly or in combination of plural kinds.

The shape of the above-mentioned layered niobate is not particularly limited. However, when the layered niobate is superposed on a plurality of layers, since it becomes difficult to be cleaved after being organicized, the thickness of the layered niobate which is not pro-organic is exhausted. It is preferable to use a thickness of one layer (about 1 nm). Further, it is preferred to use 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.

The above layered niobate is an inorganic cation which is ion exchangeable between the layers. The ion exchangeable inorganic cation refers to a metal ion such as sodium, potassium or lithium which is present on the crystal surface of the layered citrate. The plasma has ion exchange property with a cationic substance, and various substances having a cationic property can be intercalated between the layers of the above-mentioned layered niobate by an ion exchange reaction.

The cation exchange capacity (CEC) of the layered citrate is not particularly limited, and is, for example, preferably 25 to 200 meq/100 g, more preferably 50 to 150 meq/100 g, still more preferably 90 to 130 meq/100 g. As long as the cation exchange capacity of the layered niobate is 25 meq/100 g or more, a sufficient amount of the cationic substance can be intercalated between the layers of the layered niobate by ion exchange, so that the layers are sufficiently organically organicized. . On the other hand, as long as the cation exchange capacity is 200 meq/100 g or less, the bonding force between the layers of the layered niobate is not excessively strengthened, and the crystal flakes are less likely to be peeled off, and good dispersibility can be maintained.

Specific to the layered niobate satisfying the above preferred conditions For example, SUMECTON SA by KUNIMINE Industrial Co., Ltd., KUNIPIA F by KUNIMINE Industrial Co., Ltd., SOMASIF ME-100 by Co-op Chemical Co., Ltd., and LUCENTITE by Co-op Chemical Co., Ltd. Products such as STN.

In addition, as the organic sulfonate of the layered bismuth salt used in the present invention, any of the sulfonium salts can be used, and from the viewpoint of heat resistance, it is disclosed in Japanese Laid-Open Patent Publication No. 2004-107541. It is preferred that the thermal decomposition temperature is high.

The method of containing the organophilic agent between the layers of the above-mentioned layered citrate is not particularly limited, but the inorganic cation is exchanged in the organophilic agent by ion exchange reaction from the viewpoint of easy synthesis operation. It is advisable to make it contain the method. The method of ion-exchange of the ion-exchangeable inorganic cation and the organophilic agent of the layered citrate is not particularly limited, and a conventional method can be used. Specifically, it can be used for ion exchange in water, ion exchange in alcohol, ion exchange in a water/alcohol mixed solvent, and the like.

Specifically, after the layered niobate is sufficiently solvated with water or an alcohol or the like, an organophilic agent is added and stirred to replace the inorganic cation between the layers of the layered niobate with an organophilic agent. Thereafter, the unsubstituted organophilic agent was sufficiently washed, filtered, and dried. Further, the layered niobate may be directly reacted with the organic cation in an organic solvent, or the layered niobate and the organic cation may be heated and kneaded in an extruder in the presence of a resin or the like. The reaction proceeds.

The above-mentioned ion exchange can be carried out by a conventional method. To confirm. For example, a method of confirming inorganic ions exchanged in a filtrate by ICP luminescence analysis, or a method of confirming expansion of a layer interval of a layered citrate by X-ray analysis, by a heat balance from a temperature rising process The method of confirming the existence of the organophilic agent by reducing the mass, and the like, thereby confirming the substitution of the inorganic cation of the layered citrate and the organophilic agent. The ion exchange is preferably 0.05 equivalent (5% by mass) or more, more preferably 0.1 equivalent (10 mass%) or more, and still more preferably 0.5 equivalent, based on 1 equivalent of the ion-exchangeable inorganic ion of the layered niobate. (50% by mass) or more. The ion exchange is preferably carried out at a temperature of from 0 to 100 ° C, more preferably at a temperature ranging from 10 to 90 ° C, and more preferably at a temperature ranging from 15 to 80 ° C.

Further, the blending amount of the layered niobate used in the present embodiment is preferably 0.02 to 48% by mass, and more preferably 0.04 to 42% by mass based on the total amount of the composition after solvent removal. When the blending amount of the layered niobate is 0.02% by mass or more, the effect of lowering the coefficient of linear expansion can be favorably obtained. On the other hand, when it is 48 mass% or less, film formability can be improved.

By combining the cellulose nanofibers with the layered niobate and blending them, the synergistic effect is obtained, and the linear expansion coefficient can be obtained even in a small amount of blending, compared to the case where only one of the blends is blended. For significantly reduced materials. The total amount of the above-mentioned cellulose nanofibers and the layered niobate in the present state is preferably 0.1 to 80% by mass, more preferably 0.2, based on the total amount of the composition after solvent removal. ~70% by mass.

(adhesive composition)

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

Examples of the thermoplastic resin include acrylic acid, modified acrylic acid, low density polyethylene, high density polyethylene, ethylene-vinyl acetate copolymer, polyethylene terephthalate, polypropylene, modified polypropylene, and poly General purpose plastics such as styrene, acrylonitrile-butadiene-styrene copolymer, acrylonitrile-styrene copolymer, cellulose acetate, polyvinyl alcohol, polyvinyl chloride, polyvinylidene chloride, polylactic acid, etc. Indoleamine, thermoplastic polyurethane, polyacetal, polycarbonate, ultra high molecular weight polyethylene, polybutylene terephthalate, modified polyphenylene ether, polyfluorene, polyphenylene sulfide, polyether Bismuth, polyetheretherketone, polyarylate, polyetherimide, polyamidimide, liquid crystal polymer, polyamine 6T, polyamine 9T, polytetrafluoroethylene, polyvinylidene fluoride, poly The thermoplastic elastomer, the olefin-based, the styrene-based, the polyester-based, the urethane-based, the guanamine-based, the vinyl chloride-based, the hydrogenated thermoplastic elastomer, and the like are used for the steps of the ester quinone imine and the thermoplastic polyimide. .

The thermosetting resin may be any resin which can be cured by heating and exhibits electrical insulation, and examples thereof include a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, and a bisphenol S type ring. Bisphenol type epoxy resin such as oxy resin, bisphenol E type epoxy resin, bisphenol M type epoxy resin, bisphenol P type epoxy resin, bisphenol Z type epoxy resin, bisphenol A phenol type epoxy Phenolic epoxy resin such as resin, phenol novolak type epoxy resin, cresol novolac epoxy resin, biphenyl type epoxy resin, biphenyl aralkyl type epoxy resin, aryl alkylene type epoxy resin, four Hydroxyphenylethane type epoxy resin, naphthalene type epoxy resin, fluorene type epoxy resin, phenoxy type epoxy resin, dicyclopentadiene type epoxy resin, norbornene type epoxy resin, adamantane Epoxy resin, bismuth epoxy resin, glycidyl methacrylate copolymerized epoxy resin, copolymerized epoxy resin of cyclohexylmaleimide and glycidyl methacrylate, epoxy modified Polybutadiene rubber derivative, CTBN modified epoxy resin, trimethylolpropane polyglycidyl ether, phenyl-1,3 - diglycidyl ether, biphenyl-4,4'-diglycidyl ether, 1,6-hexanediol diglycidyl ether, diglycidyl ether of ethylene glycol or propylene glycol, sorbitol polyglycidyl ether , ginseng (2,3-epoxypropyl)isocyanurate, triglycidyl ginseng (2-hydroxyethyl)isocyanurate, phenolic novolac resin, cresol novolac resin, bisphenol A phenolic resin, etc. Resin type phenol resin, unmodified phenolic phenolic resin, refinable phenol resin modified with tung oil, linseed oil, walnut oil, etc. a triazine ring-containing resin such as a phenol resin, a phenoxy resin, a urea resin, a melamine resin, an unsaturated polyester resin, a bismaleimide resin, or diallyl phthalate Resin, polyoxyn resin, with benzo Ring resin, norbornene resin, cyanate resin, isocyanate resin, urethane resin, benzocyclobutene resin, maleimide resin, bismaleimide triazine resin, poly A methylimine resin, a thermosetting polyimine, or the like.

The radically polymerizable photocurable resin may be a resin which can be cured by irradiation with an active energy ray and exhibits electrical insulating properties, and a compound having one or more ethylenically unsaturated bonds in the molecule is used. The object is preferred. As the compound having an ethylenically unsaturated bond, a known photopolymerizable oligomer, a photopolymerizable vinyl monomer, or the like can be used.

Examples of the photopolymerizable oligomer include an unsaturated polyester oligomer and a (meth)acrylate oligomer. Examples of the (meth) acrylate-based oligomer include phenol novolac epoxy (meth) acrylate, cresol novolac epoxy (meth) acrylate, and bisphenol epoxy (meth) acrylate. Epoxy (meth) acrylate, urethane (meth) acrylate, epoxy urethane (meth) acrylate, polyester (meth) acrylate, polyether (A Acrylate, polybutadiene modified (meth) acrylate, and the like. Further, in the present specification, the term "(meth)acrylate" refers to the term "acrylate", methacrylate, and the like, and the other similar expressions are also the same.

As the photopolymerizable vinyl monomer, a known one may be used, and examples thereof include a styrene derivative such as styrene, chlorostyrene or α-methylstyrene; vinyl acetate, vinyl butyrate or benzoic acid; Vinyl esters such as vinyl ester; vinyl isobutyl ether, vinyl-n-butyl ether, vinyl-t-butyl ether, vinyl-n-pentyl ether, vinyl isoamyl ether, ethylene Vinyl ethers such as benzyl-n-octadecyl ether, vinyl cyclohexyl ether, ethylene glycol monobutyl vinyl ether, triethylene glycol monomethyl vinyl ether; acrylamide, methacryl Indoleamine, N-hydroxymethylpropenylamine, N-hydroxymethylmethacrylamide, N-methoxymethylpropenylamine, N-ethoxymethylpropenamide, N-butoxy (meth) acrylamide such as methacrylamide; allyl compound such as triallyl isocyanurate, diallyl phthalate or diallyl isophthalate ; 2-ethylhexyl (meth)acrylate Ester, lauryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, phenyl (meth)acrylate, phenoxyethyl (meth)acrylate, etc. An ester of methyl acrylate; a hydroxyalkyl (meth) acrylate such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate or neopentyl alcohol 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-hexanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylic acid Ester alkyl polyol (meth) acrylate such as ester, pentaerythritol tetra(meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc.; diethylene glycol di(methyl) Polyoxyalkylene oxides such as acrylate, triethylene glycol di(meth)acrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane tri(meth)acrylate Poly(methyl) propylene Poly(meth)acrylates such as hydroxytrimethylacetic acid neopentyl glycol di(meth)acrylate; and [(meth)acryloxyethyl]isocyanurate Isocyanurate type poly(meth) acrylates and the like.

As the cationically polymerizable photocurable resin, an alicyclic epoxy compound, an oxetane compound, a vinyl ether compound or the like can be preferably used. Among them, examples of the alicyclic epoxy compound include 3,4,3',4'-dicyclooxybicyclohexyl, 2,2-bis(3,4-epoxycyclohexyl)propane, and 2 , 2-bis(3,4-epoxycyclohexyl)-1,3-hexafluoropropane, bis(3,4-epoxycyclohexyl)methane, 1-[1,1-bis(3,4 -Epoxycyclohexyl)]ethylbenzene, bis(3,4-epoxycyclohexyl)adipate, 3,4-epoxycyclohexyl Methyl (3,4-epoxy)cyclohexylcarboxylate, (3,4-epoxy-6-methylcyclohexyl)methyl-3',4'-epoxy-6-methyl ring Hexyl carboxylate, ethyl-1,2-bis(3,4-epoxycyclohexylcarboxylic acid) ester, epoxycyclohexane, 3,4-epoxycyclohexylmethyl alcohol, 3, An epoxy group-containing alicyclic epoxy compound such as 4-epoxycyclohexylethyltrimethoxydecane. As a commercial item, for example, CELOXIDE 2000, CELOXIDE 2021, CELOXIDE 3000, EHPE 3150 manufactured by DAICEL Chemical Industry Co., Ltd.; EPOMIK VG-3101 manufactured by Mitsui Chemicals Co., Ltd.; E-1031S manufactured by Yuka Shell Epoxy Co., Ltd.; Mitsubishi TETRAD-X, TETRAD-C manufactured by Gas Chemical Co., Ltd.; EPB-13, EPB-27, etc. manufactured by Japan Soda Co., Ltd.

As an oxetane compound, in addition to bis[(3-methyl-3-oxetanylmethoxy)methyl]ether, bis[(3-ethyl-3-oxetanylmethoxy)methyl Ether, 1,4-bis[(3-methyl-3-oxetanylmethoxy)methyl]benzene, 1,4-bis[(3-ethyl-3-oxetanylmethoxy) Methyl]benzene, (3-methyl-3-oxetanyl)methacrylate, (3-ethyl-3-oxetanyl)methacrylate, (3-methyl-3) -oxetanyl)methyl methacrylate, (3-ethyl-3-oxetanyl)methyl methacrylate or polyfunctional oxalates of such oligomers or copolymers Examples of the cyclobutanes include oxetane and phenol resins, poly(p-hydroxystyrene), cardo type bisphenols, calixarenes, and resorcinol calixarenes (calix resorcinarene). Or an oxetane such as an ether compound of a resin having a hydroxyl group, a copolymer of an unsaturated monomer having an oxetane ring, and an alkyl (meth)acrylate, such as a silsesquioxane. Compound. As a commercial item, for example, Eternacoll OXBP, OXMA, OXBP, EHO, and 茬, manufactured by Ube Industries Co., Ltd. X-ray bisoxetane, ARON OXETANE OXT-101, OXT-201, OXT-211, OXT-221, OXT-212, OXT-610, PNOX-1009, etc., manufactured by East Asia Synthetic Co., Ltd.

Examples of the vinyl ether compound include cyclic ether type vinyl ethers such as isosorbide divinyl ether and oxanordecene divinyl ether (oxirane ring, oxetane ring, a vinyl ether having a cyclic ether group such as an oxolane ring; an aryl vinyl ether such as a phenyl vinyl ether; an alkyl group such as n-butyl vinyl ether or octyl vinyl ether; Vinyl ether; cycloalkyl vinyl ether such as cyclohexyl vinyl ether; hydroquinone divinyl ether, 1,4-butanediol divinyl ether, cyclohexyl divinyl ether, cyclohexane dimethanol A polyfunctional vinyl ether such as vinyl ether or a vinyl ether compound having a substituent such as an alkyl group or an allyl group at the α and/or β position. As a commercial item, 2-hydroxyethyl vinyl ether (HEVE), diethylene glycol monovinyl ether (DEGV), 2-hydroxybutyl vinyl ether (made by Maruzen Petrochemical Co., Ltd.) are mentioned, for example. HBVE), triethylene glycol divinyl ether, and the like.

Further, when the printed wiring board material of the present embodiment is used as an alkali-developing photosensitive resist which can be developed with an aqueous alkali solution, a carboxyl group-containing resin is preferably used as the binder component.

(resin containing carboxyl group)

As the carboxyl group-containing resin, a photosensitive carboxyl group-containing resin having one or more photosensitive unsaturated double bonds and a carboxyl group-containing resin having no photosensitive unsaturated double bond can be used. As the resin containing a carboxyl group, those exemplified in the above state can be preferably used.

In the printed wiring board material of this form, in addition to the cellulose nanofiber, the binder component, and the layered niobate, other conventionally synthesized components can be suitably blended according to the use thereof.

As another conventional compounding component, a curing catalyst, a photopolymerization initiator, a coloring agent, an organic solvent, etc. are mentioned, for example.

The hardening catalyst is one in which the thermosetting resin is mainly cured in the curable resin, and examples of the curing catalyst include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methyl group. Imidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole Imidazole derivatives; dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethyl An amine compound such as benzylamine or 4-methyl-N,N-dimethylbenzylamine; an anthracene compound such as diammonium adipate or diterpene sebacate; or a phosphorus compound such as triphenylphosphine Wait. Moreover, as a commercial item, 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (made by Shikoku Chemical Industry Co., Ltd.), U-CAT3503N, U-CAT3502T, DBU, DBN, U-CATSA102 are mentioned, for example. U-CAT5002 (San-Apro) can be used alone or in combination of two or more. Similarly, guanamine, acetammine, benzoguanamine, melamine, 2,4-diamino-6-methylpropenyloxyethyl-S-triazine, 2-ethylene can also be used. Benzyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine ‧ isocyanuric acid adduct, 2,4-diamino group An S-triazine derivative such as a 6-methylpropenyl methoxyethyl-S-triazine ‧ isocyanuric acid addition product.

Further, the photopolymerization initiator is among the curable resins, the main In order to cure the photocurable resin, examples of the photopolymerization initiator include 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, Acetophenones such as 1,1-dichloroacetophenone; 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylpropan-1-one, 2-benzyl -2-Dimethylamino-1-(4-morpholinylphenyl)-butanone-1, 2-(dimethylamino)-2-[(4-methylphenyl)methyl] Aminoalkylphenones such as 1-[4-(4-ythyl)phenyl]-1-butanone; 2-methylindole, 2-ethylanthracene, 2-tert-butyl Anthraquinones such as guanidine and 1-chloroindole; 2,4-dimethylthiothioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-di a thioxanthone such as isopropyl thioxanthone; a ketal such as acetophenone dimethyl ketal or benzyl dimethyl ketal; a diphenyl ketone such as diphenyl ketone; or thioxan Ketones; (2,6-dimethoxybenzylidene)-2,4,4-pentylphosphine oxide, bis(2,4,6-trimethylbenzylindenyl)-phenylphosphine oxide , phosphine oxides such as 2,4,6-trimethylbenzylnonyldiphenylphosphine oxide, ethyl-2,4,6-trimethylbenzylnonylphenylphosphinate; various peroxides Classes, titanocene initiators, and the like. These may also be used in combination with ethyl N,N-dimethylaminobenzoate, isoamyl N,N-dimethylaminobenzoate, pentyl-4-dimethylaminobenzoate, A photo-sensitizer of a tertiary amine such as triethylamine or triethanolamine. These photopolymerization initiators may be used singly or in combination of two or more.

As the coloring agent, as exemplified in the above state, a known exemplified by chromaticity as a coloring pigment or a dye can be used.

As an organic solvent, it can be exemplified in the first state. By.

Further, an additive such as an antifoaming ‧ leveling agent, a thixotropic imparting agent ‧ a tackifier, a coupling agent, a dispersing agent, a flame retardant, etc. may be used as needed.

As the antifoaming agent, the leveling agent, the coupling agent, the dispersing agent, and the flame retardant, those exemplified in the first state can be used.

As the thixotropic imparting agent ‧ tackifier, fine particles such as vermiculite, vermiculite gel, amorphous inorganic particles, polyamine-based additives, modified urea-based additives, wax-based additives, and the like can be used.

The other synthetic component may, for example, be a photoacid generator such as a photoacid generator such as an azo salt, a phosphonium salt or an iodonium salt, an amine formate compound, an α-aminoketone compound or an O-indenyl ruthenium compound. Agent, inorganic filler such as barium sulfate or spheroidal vermiculite, organic filler such as tantalum powder, nylon powder, fluorine powder, radical scavenger, ultraviolet absorber, peroxide decomposer, thermal polymerization inhibitor, adhesion promotion Agent, rust inhibitor, etc.

The printed wiring board material according to the present embodiment, which is configured as described above, can be suitably used for a solder resist and a core material, and can be suitably used for an interlayer insulating material of a multilayer printed wiring board. The desired effect of this state can be obtained in the printed wiring board. Further, when the present embodiment is applied to a printed wiring board material, for example, the cellulose nanofibers may be formed into a sheet shape, and the binder component may be impregnated into the flaky cellulose nanofibers and dried. The method of making a prepreg.

Fig. 1 is a partial cross-sectional view showing a configuration example of a multilayer printed wiring board according to the present aspect. The multilayer printed wiring board shown can be For example, the manufacturing is carried out as follows. First, a through hole is formed in the core substrate 2 on which the conductor pattern 1 is formed. The formation of the through holes can be performed by appropriate means such as drilling or die punching, laser light or the like. Thereafter, a roughening agent is used for the roughening treatment. In general, the roughening treatment is an organic solvent such as N-methyl-2-pyrrolidone, N,N-dimethylformamide or methoxypropanol, or a base such as caustic soda or caustic potash. The aqueous solution or the like is swelled, and is carried out using an oxidizing agent such as dichromate, permanganate, ozone, hydrogen peroxide/sulfuric acid, or nitric acid.

Next, the conductor pattern 3 is formed by combining electroless plating, electrolytic plating, or the like. The step of forming the conductor layer by electroless plating is a step of immersing in an aqueous solution containing a plating catalyst, absorbing the catalyst, and then immersing it in the plating solution to deposit the plating. According to the conventional method (elimination processing 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 in the figure, the conductor pattern 3 is formed on both sides. At this time, a plating layer is also formed in the through hole, and as a result, the joint portion 4 of the conductor pattern 3 of the multilayer printed wiring board and the joint portion 1a of the conductor pattern 1 are electrically connected to each other. A through hole 5 is formed.

Then, the thermosetting composition is applied, for example, by a screen printing method, a spray coating method, a shower coating method, or the like, and then heat-cured to form the interlayer insulating layer 6. When a dry film or a prepreg is used, it is heat-hardened by lamination or hot plate pressing to form an interlayer insulating layer 6. Next, a via hole 7 for electrically connecting the joint portions of the respective conductor layers is formed by an appropriate means such as laser light. Forming, the conductor pattern 8 is formed in the same manner as the conductor pattern 3 described above. Further, the interlayer insulating layer 9, the via hole 10, and the conductor pattern 11 are formed in the same manner. Thereafter, the solder resist layer 12 is formed on the outermost layer, thereby manufacturing a multilayer printed wiring board. Although the above description has been made on the case where the interlayer insulating layer and the conductor layer are formed on the laminated substrate, a single-sided substrate or a double-sided substrate may be used instead of the laminated substrate.

[Third aspect of the invention]

The printed wiring board material of this embodiment may be one or both of a cellulose nanofiber including a binder component, a number average fiber diameter of 3 nm to 1000 nm, a polyfluorene oxide compound, and a fluorine compound.

As the cellulose nanofiber, the same state as in the first embodiment can be used.

The average fiber diameter of the cellulose nanofibers in the present state must 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 cellulose nanofiber single fiber is 3 nm, substantially less than 3 nm cannot be produced, and when it exceeds 1000 nm, the dispersibility with the binder component is deteriorated. In addition, the average fiber diameter of the cellulose nanofibers is observed by a SEM (Scanning Electron Microscope) or a TEM (Transmission Electron Microscope), and is pulled out diagonally on the photograph. Straight lines were randomly drawn from the fibers near the line at 12 o'clock. After removing the coarsest fibers and the finest fibers, the remaining 10 points were measured and the average value was taken.

The blending amount of the above cellulose nanofibers in the present state, The amount of the composition after removal of the solvent is preferably from 0.1 to 80% by mass, more preferably from 0.2 to 70% by mass. When the blending amount of the cellulose nanofiber is 0.1% by mass or more, the desired effect of the present state can be favorably obtained. On the other hand, when it is 80 mass% or less, film formability can be improved.

(polyoxyl compound)

Examples of the polyfluorene oxide compound include polydimethyl methoxy olefin, polyalkyl phenyl siloxane, alkyl modified polyoxy olefin oil, polyether modified poly oxirane oil, and polyalkyl hydrazine. Oxane, polymethylsesquioxanes, polyalkylhydroquinones, polyalkylenyloxyoxanes, polymethylphenyloxiranes, aralkyl modified polyoxyxides, alkyl An aralkyl modified polyoxyphthalic acid or the like. As a commercial item, for example, BYK-300, BYK-302, BYK-306, BYK-307, BYK-310, BYK-313, BYK-330, BYK-331, BYK-333, BYK-337, BYK can be cited. -341, BYK-344, BYK-370, BYK375 (above, BYK-CHEMIE JAPAN (share) system), 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, 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, Shin-Etsu Chemical Co., Ltd.).

(fluorine compound)

The fluorine compound may, for example, be a fluorine-based resin having a perfluoroalkyl group or a perfluoroalkenyl group in the molecule. As a commercial item, for example, MEGAFAC F-444, the same F-472, the same F-477, the same F-552, the same F-553, the same F-554, the same F-443, the same F-470, the same F-470, the same F-475, the same F-482, the same F-483, the same F-489, the same R-30, the same RS-75 (above, DIC (share) system), EFTOP EF301, the same 303, the same 352 (above, new Akita Chemicals Co., Ltd.), Fluorad FC-430, FC-431 (above, Sumitomo 3M (share) system), ASAHI GUARD AG-E300D, Surflon S-382, same as SC-101, same SC-102, the same SC-103, the same SC-104, the same SC-105, the same SC-106 (above, Asahi Glass Co., Ltd.), BM-1000, BM-1100 (above, Yushang (share) system) , NBX-15, FTX-218 (above, (share) NEOS system).

The blending amount of one or both of the above-mentioned polyfluorene oxide compound and 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 based on 100 parts by mass of the binder component. The mass fraction is more preferably 0.05 to 3 parts by mass. When the blending amount of either or both of the polyoxo compound and the fluorine compound is 0.01% by mass or more, the desired effect in the present state can be favorably obtained. On the other hand, when it is 20 mass% or less, film formability can be improved.

(adhesive composition)

As the binder component used in this embodiment, the same as the second aspect can be used.

(resin containing carboxyl group)

Further, when the printed wiring board material of the present embodiment is used as an alkali-developing photosensitive resist which can be developed with an aqueous alkali solution, a carboxyl group-containing resin is preferably used as the binder component.

As the resin containing a carboxyl group, the same as the second aspect can be used.

In the printed wiring board material of the present embodiment, in addition to the cellulose nanofiber, the binder component, and either or both of the polyoxo compound and the fluorine compound, other conventionally synthesized components may be suitably blended depending on the use thereof.

As another conventional compounding component, a curing catalyst, a photopolymerization initiator, a coloring agent, an organic solvent, etc. are mentioned, for example.

As such a curing catalyst, a photopolymerization initiator, a colorant, and an organic solvent, those exemplified in the second aspect can be used.

Further, an additive such as an antifoaming ‧ leveling agent, a thixotropic imparting agent ‧ a tackifier, a coupling agent, a dispersing agent, a flame retardant, etc. may be used as needed.

As a defoaming agent ‧ leveling agent, mineral oil, vegetable oil, aliphatic alcohol, fatty acid, metal soap, fatty acid decylamine, polyoxyalkylene glycol, polyoxyalkylene alkyl ether, A compound such as a polyoxyalkylene fatty acid ester or the like.

As the thixotropic imparting agent ‧ tackifier, coupling agent, dispersing agent, and flame retardant, those exemplified in the first embodiment can be used.

As another compounding component, for example, an azo salt or a hydrazine can be mentioned. a photoacid generator such as a salt or an iodonium salt, a carbamate compound, an α-amino ketone compound, a photobase generator such as an O-indenyl hydrazine compound, barium sulfate, globular vermiculite, hydrotalcite, or the like. Organic fillers such as inorganic fillers, niobium powder, nylon powder, and fluorine powder, radical scavengers, ultraviolet absorbers, peroxide decomposers, thermal polymerization inhibitors, adhesion promoters, rust inhibitors, and the like.

The printed wiring board material according to the present embodiment, which is configured as described above, can be suitably used for an interlayer insulating material of a multilayer printed wiring board, and can be suitably used for the obtained printed wiring. The desired effect of this state can be obtained in the board. Further, when the present embodiment is applied to a printed wiring board material, for example, the cellulose nanofibers may be formed into a sheet shape, and the binder component, and the polyoxonium compound and the fluorine compound may be used. A method in which a composition obtained by one or both of the layers is impregnated into the flaky cellulose nanofibers and dried to prepare a prepreg.

The multilayer printed wiring board of the present aspect as shown in Fig. 1 can be manufactured in the same manner as the second aspect.

[Fourth aspect of the invention]

The printed wiring board material of the present invention may be a cellulose fiber including a binder component, a number average fiber diameter of 1 μm or more, and a cellulose nanofiber having a number average fiber diameter of 3 nm or more and less than 1000 nm.

(Cellulose fiber and cellulose nanofiber)

The above cellulose fiber and cellulose nanofiber can be obtained as follows Got it.

The raw material of the cellulose fiber and the cellulose nanofiber can be exemplified in the same manner as in the first embodiment.

In order to produce cellulose fibers from the above raw materials, a method of applying knocking to pulverization treatment may be used for the above-mentioned raw materials.

In the pulverization treatment, for example, the pulp or the like is mechanically treated by a high-pressure homogenizer or the like to be loosened to a fiber diameter of about 1 to 10 μm, and an aqueous suspension of about 0.1 to 3% by mass is obtained. Cellulose fiber.

Further, in order to produce the cellulose nanofiber from the above-mentioned raw material, after the above-mentioned raw material is knocked to the pulverization treatment, the method of applying the grinding to the pulverization treatment, or the high-temperature high-pressure steam treatment, the phosphate, or the like is used. The processing of the above materials can loosen the above raw materials to the nanometer size.

In the above, the cellulose fiber obtained by knocking down to the pulverization treatment is repeatedly pulverized by a grinder or the like to obtain a cellulose nanofiber having a fiber diameter of about 10 to 100 nm. Rice fiber.

The above-described grinding to pulverization treatment, the above-described high-temperature high-pressure steam treatment, and the above-described treatment with phosphate or the like can be carried out in the same manner as in the first embodiment.

Further, the cellulose fibers and the cellulose nanofibers used in the present embodiment may be chemically modified and/or physically modified in the same manner as in the first embodiment to improve the functionality.

Cellulose fiber and cellulose nanoparticle used in this state The average fiber diameter of the fiber is the value obtained in the same manner as the first state.

The number average fiber diameter of the cellulose nanofibers used in this embodiment must be 3 nm or more and less than 1000 nm, preferably 3 nm to 200 nm, more preferably 3 nm to 100 nm. Since the minimum diameter of the cellulose nanofiber single fiber is 3 nm, it is substantially impossible to manufacture less than 3 nm, and when it exceeds 1000 nm, the desired effect cannot be obtained.

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

In the present state, in the process of preparing the cellulose nanofibers, when the fibers are loosened to the nanometer size, the treatment is stopped even in the middle, and the entire amount is not loosened, and the above remains. A cellulose fiber having a number of average fiber diameters, whereby a mixture of cellulose fibers and cellulose nanofibers satisfying the conditions of the present state can be obtained. Therefore, in the printed wiring board material of the present aspect, in addition to the cellulose fibers and the cellulose nanofibers satisfying the specific number average fiber diameter range, the number average fiber diameter other than the specific average fiber diameter range may be included. Cellulose fiber.

The cellulose fiber may be a condition that satisfies the above-described number average fiber diameter, and a commercially available product can be suitably used, and it is not particularly limited.

According to this aspect, by combining the above cellulose fibers with the upper The cellulose nanofibers are blended and blended to achieve excellent peel strength which has not been conventionally obtained. The mass ratio of the above cellulose fibers to the above cellulose nanofibers in the present state is preferably from 9:1 to 1:9, more preferably from 8:2 to 2:8. By setting it as this range, a higher peeling strength can be obtained.

The total amount of the cellulose fibers and the cellulose nanofibers in the present embodiment is preferably from 0.5 to 80% by mass, more preferably from 1 to 1%, based on the total amount of the composition after solvent removal. 70% by mass. When the total amount of the cellulose fibers and the cellulose nanofibers blended is 0.5% by mass or more, a higher peel strength can be obtained, and by setting the content to 80% by mass or less, good film formability can be obtained. .

(adhesive composition)

As the binder component used in this embodiment, the same as the second aspect can be used.

(resin containing carboxyl group)

Further, when the printed wiring board material of the present embodiment is used as an alkali developing type insulating material which can be developed with an aqueous alkali solution, a resin containing a carboxyl group is preferably used as the binder component.

As the resin containing a carboxyl group, the same as the second aspect can be used.

In the printed wiring board material of the present state, in addition to the cellulose fiber, the cellulose nanofiber, and the binder component, other conventional synthetic components, such as a curing catalyst, a photopolymerization initiator, may be suitably blended according to the use thereof. A coloring agent, an organic solvent, or the like.

As such a curing catalyst, a photopolymerization initiator, a colorant, and an organic solvent, those exemplified in the second aspect can be used.

Further, an additive such as an antifoaming ‧ leveling agent, a thixotropic imparting agent ‧ a tackifier, a coupling agent, a dispersing agent, a flame retardant, etc. may be used as needed.

As the defoaming agent, the leveling agent, the thixotropic imparting agent, the tackifier, the coupling agent, the dispersing agent, and the flame retardant, those exemplified in the first state can be used.

The other synthetic component may, for example, be a photoacid generator such as a photoacid generator such as an azo salt, a phosphonium salt or an iodonium salt, an amine formate compound, an α-aminoketone compound or an O-indenyl ruthenium compound. Agent, barium sulfate, spheroidal vermiculite, hydrotalcite and other inorganic fillers, antimony powder, nylon powder, organic powder such as fluorine powder, radical scavenger, ultraviolet absorber, peroxide decomposer, thermal polymerization inhibitor, Adhesion promoter, rust inhibitor, etc.

The printed wiring board material according to the present aspect configured as described above can be suitably used for the interlayer insulating material of the core material and the multilayer printed wiring board, whereby the obtained printed wiring board can be obtained. The desired effect. Further, when the present embodiment is applied to a printed wiring board material, for example, a mixture of the cellulose fibers and the cellulose nanofibers may be formed into a sheet shape, and the binder component may be impregnated into the sheet and dried. The method of making a prepreg.

The multilayer printed wiring board of the present aspect as shown in Fig. 1 can be manufactured in the same manner as the second aspect.

[Fifth aspect of the invention]

The printed wiring board material of this embodiment may be a cellulose nanofiber including a binder component and a number average fiber diameter of 3 nm to 1000 nm having a carboxylate in the structure. Such a cellulose nanofiber is obtained by making the natural cellulose fiber oxidized and then miniaturizing it.

(cellulose nanofibers with carboxylate in the structure)

First, the natural cellulose fibers are dispersed in water of about 10 to 1000 times (mass basis) on an absolute dry basis using a mixer or the like to prepare an aqueous dispersion. Examples of the natural cellulose fiber which is a raw material of the cellulose nanofibers include non-wood pulp, cotton linters or cotton linters such as wood pulp such as conifer pulp or hardwood pulp, straw pulp or bagasse pulp. Such as cotton pulp, bacterial cellulose and the like. These may be used alone or in combination of two or more. Further, the natural cellulose fibers may be subjected to a treatment such as knocking to increase the surface area.

Next, an N-oxyl compound is used as an oxidation catalyst in the aqueous dispersion to carry out oxidation treatment of natural cellulose fibers. As such an N-oxyl compound, for example, TEMPO (2,2,6,6-tetramethylpiperidine-N-hydrocarbyloxy), 4-carboxy-TEMPO, 4-acetamide can be used. -TEMPO, 4-amino-TEMPO, 4-dimethylamino-TEMPO, 4-phosphinooxy-TEMPO, 4-hydroxy TEMPO, 4-oxy TEMPO, 4-methoxy TEMPO, 4-( A TEMPO derivative having various functional groups at the C4 position, such as 2-bromoacetamide)-TEMPO or 2-azaadamantane N-hydrocarbyloxy group. As such N-oxyl compounds The amount of addition is sufficient in terms of the amount of the catalyst, and is usually in the range of 0.1 to 10% by mass based on the absolute dry basis with respect to the natural cellulose fibers.

In the oxidation treatment of the above natural cellulose fibers, an oxidizing agent and a co-oxidizing agent are used in combination. Examples of the oxidizing agent include a halous acid, a hypohalous acid, a perhalogen acid, and the like, a salt thereof, a hydrogen peroxide, a perorganic acid, and an alkali metal hypohalous acid such as sodium hypochlorite or sodium hypobromite. Salt is preferred. Further, as the co-oxidizing agent, an alkali metal bromide such as sodium bromide can be used. The amount of the oxidizing agent to be used is usually in the range of about 1 to 100% by mass based on the absolute dry basis, and the amount of the co-oxidizing agent is usually about 1 based on the absolute dry basis with respect to the natural cellulose fiber. ~30% by mass range.

In the oxidation treatment of the above natural cellulose fibers, it is preferred to maintain the pH of the aqueous dispersion in the range of 9 to 12 in order to carry out the oxidation reaction efficiently. Further, the temperature of the aqueous dispersion at the time of the oxidation treatment can be arbitrarily set within the range of 1 to 50 ° C, and the reaction can be carried out at room temperature without temperature control. The reaction time can be set in the range of 1 to 240 minutes. Further, in the aqueous dispersion, a permeating agent may be added in order to allow the agent to permeate into the inside of the natural cellulose fiber so that more carboxyl groups are introduced to the surface of the fiber. Examples of the penetrating agent include an anionic surfactant such as a carboxylate, a sulfate salt, a sulfonate or a phosphate salt, or a nonionic surfactant such as a polyethylene glycol type or a polyol type.

After the oxidation treatment of the natural cellulose fibers, it is preferred to carry out a purification treatment for removing impurities such as unreacted oxidizing agents or various by-products contained in the aqueous dispersion before the miniaturization. Specifically For example, a method of repeatedly washing and filtering the oxidized natural cellulose fibers can be used. The natural cellulose fiber obtained by the purification treatment is usually supplied to the micronization treatment in a state of being impregnated with an appropriate amount of water, and may be dried to be in a fibrous or powder form as needed.

Then, the natural cellulose treatment is refined, and the natural cellulose fibers after the purification treatment are desirably dispersed in a solvent such as water. As a solvent for the dispersion medium used in the refining treatment, water is usually preferred, but alcohol (methanol, ethanol, isopropanol, isobutanol, sec-butanol, tert) may be used as desired. -butanol, methyl sarcolo, ethyl sirolius, ethylene glycol, glycerol, etc.) or ethers (ethylene glycol dimethyl ether, 1,4-dioxane, tetrahydrofuran, etc.), ketones ( A water-soluble organic solvent such as acetone, methyl ethyl ketone, N,N-dimethylformamide, N,N-dimethylacetamide or dimethyl hydrazine, etc., may also be used. These mixtures. The solid content of the natural cellulose fibers in the dispersion of the solvent is preferably 50% by mass or less. When the solid content of the natural cellulose fibers exceeds 50% by mass, it is not preferable because extremely high energy is required for dispersion. For the refinement of natural cellulose treatment, a low pressure homogenizer, a high pressure homogenizer, a grinder, a cutting pulverizer, a ball mill, a jet mill, a knocking machine, a disintegrator, a short shaft extruder, a twin shaft extruder, It is carried out by a dispersing device such as an ultrasonic mixer or a household juicer mixer.

The cellulose nanofiber obtained by the micronization treatment can be made into an adjusted suspension having a solid content concentration as desired. Shaped, or made a dry powder. Here, when it is in the form of a suspension, water may be used as the dispersion medium, and water and another organic solvent, for example, an alcohol such as ethanol or a mixed solvent of a surfactant, an acid, an alkali or the like may be used.

By the oxidation treatment and the refinement treatment of the natural cellulose fibers, the hydroxyl group at the C6 position of the constituent unit of the cellulose molecule is selectively oxidized to a carboxyl group via the aldehyde group, and the content of the carboxyl group is such that The high crystalline cellulose nanofiber of the above specified number average fiber diameter formed by the cellulose molecules of 0.1 to 3 mmol/g. This highly crystalline cellulose nanofiber has a cellulose I type crystal structure. This means that such a cellulose nanofiber is a surface oxidized and refined by a natural cellulose molecule having a type I crystal structure. That is, in the process of biosynthesis, the natural cellulose fiber is formed into a high-order solid structure by multi-bundling the microfibers called microfibrils to form a strong aggregation force between the microfibers ( The hydrogen bond between the surfaces is introduced into the aldehyde group or the carboxyl group by oxidation treatment to weaken it, and further, the cellulose nanofiber is obtained by the miniaturization treatment. By adjusting the conditions of the oxidation treatment, the content of the carboxyl group is increased or decreased, or the polarity is changed, and the average fiber diameter or the average fiber length and the average aspect of the cellulose nanofiber can be controlled by electrostatic repulsion or miniaturization treatment of the carboxyl group. Than wait.

It is judged that the natural cellulose fiber is a type I crystal structure, and in a diffraction profile obtained by measurement of the wide-angle X-ray diffraction image, in the vicinity of 2θ=14 to 17° and 2θ=22 to 23 The two positions near ° have typical peaks, whereby the natural cellulose fibers can be identified as a type I crystalline structure. Further, when a carboxyl group is introduced into the cellulose molecule of the cellulose nanofiber, it is confirmed whether or not the carbonyl group is absorbed in the total reflection type infrared spectroscopy (ATR) by the sample in which the water is completely removed (1608 cm). The existence of ^-1 nearby). In the case of a carboxyl group (COOH), there was absorption at 1730 cm ^-1 in the above measurement.

Further, since the natural cellulose fibers after the oxidation treatment are adhered or bonded with a halogen atom, the halogen removal treatment can be carried out for the purpose of removing such residual halogen atoms. The dehalogenation treatment can be carried out by immersing the oxidized natural cellulose fibers in a hydrogen peroxide solution or an ozone solution.

Specifically, for example, the natural cellulose fiber after the oxidation treatment is immersed in a concentration of 0.1 at a bath ratio of about 1:5 to 1:100, preferably about 1:10 to 1:60 (mass ratio). ~100g / L in hydrogen peroxide solution. The concentration of the hydrogen peroxide solution at this time is preferably from 1 to 50 g/L, more preferably from 5 to 20 g/L. Further, the pH of the hydrogen peroxide solution is preferably from 8 to 11, more preferably from 9.5 to 10.7.

Further, the weight of the cellulose nanofibers contained in the aqueous dispersion relative to the amount of carboxyl groups in the cellulose [mmol/g] 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 having a dry weight of a fine scale was prepared, and the pH was adjusted to about 2.5 by a 0.1 M aqueous hydrochloric acid solution, and then a 0.05 M aqueous sodium hydroxide solution was dropped thereto. The pH was about 11 and the conductivity was measured. The amount of sodium hydroxide (V) consumed in the neutralization step of the weak acid which is moderated by the change in conductivity can be determined by the following formula. The amount of this functional group is the amount representing a carboxyl group.

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

The number average fiber diameter of the cellulose nanofibers used in this embodiment must 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 cellulose nanofiber single fiber is 3 nm, it is substantially impossible to manufacture less than 3 nm, and when it exceeds 1000 nm, in order to obtain the desired effect of the present invention, it is necessary to add an excessive amount to deteriorate the film forming property. . In addition, the average fiber diameter of the cellulose nanofibers is observed by a SEM (Scanning Electron Microscope) or a TEM (Transmission Electron Microscope), and is pulled out diagonally on the photograph. Straight lines were randomly drawn from the fibers near the line at 12 o'clock. After removing the coarsest fibers and the finest fibers, the remaining 10 points were measured and the average value was taken.

In the printed wiring board material of the present invention, the blending amount of the cellulose nanofiber is preferably 0.1 to 80% by mass, more preferably 0.2 to 70% by mass based on the total amount of the composition after removing the solvent. . When the blending amount of the cellulose nanofiber is 0.1% by mass or more, the desired effect of the present state can be favorably obtained. On the other hand, when it is 80 mass% or less, film formability can be improved.

(adhesive composition)

As the binder component used in this embodiment, the same as the second aspect can be used.

(resin containing carboxyl group)

Further, when the printed wiring board material of the present embodiment is used as an alkali-developing photosensitive resist which can be developed with an aqueous alkali solution, a carboxyl group-containing resin is preferably used as the binder component.

As the resin containing a carboxyl group, the same as the second aspect can be used.

In the printed wiring board material of this form, in addition to the cellulose nanofiber and the binder component, other conventional compounding points can be suitably blended according to the use thereof.

As another conventional compounding component, for example, an elastomer having a functional group may be added to the printed wiring board material of the present aspect. The trade name of the elastomer having a functional group may, for example, be R-45HT, Poly bd HTP-9 (manufactured by Idemitsu Kosan Co., Ltd.), EPOLEAD PB3600 (manufactured by DAICEL), or DENALEX R-45EPT (NAGASE CHEMTEX). (share)), Ricon 130, Ricon 131, Ricon 134, Ricon 142, Ricon 150, Ricon 152, Ricon 153, Ricon 154, Ricon 156, Ricon 157, Ricon 100, Ricon 181, Ricon 184, Ricon 130MA8, Ricon 130MA13 Ricon 130MA20, Ricon 131MA5, Ricon 131MA10, Ricon 131MA17, Ricon 131MA20, Ricon 184MA6, Ricon 156MA17 (manufactured by SARTOMER), etc., polyester elastomer, polyurethane elastomer, polyester amine base can be used. A formate elastomer, a polyamide-based elastomer, a polyester amide-based elastomer, an acrylic elastomer, an olefin-based elastomer, or the like. Further, a resin obtained by modifying a part or all of an epoxy group having various skeletons, and a resin modified with a carboxylic acid-modified butadiene-acrylonitrile rubber having two kinds of ends may be used. Further, an epoxy-containing polybutadiene-based elastomer or propylene-containing material may also be used. An acid polybutadiene-based elastomer, a hydroxyl group-containing polybutadiene-based elastomer, a hydroxyl group-containing isoprene-based elastomer, or the like. These elastic materials may be used alone or in combination of two or more.

As other components, a thermosetting catalyst, a photopolymerization initiator, a colorant, and an organic solvent may be added.

As such a curing catalyst, a photopolymerization initiator, a colorant, and an organic solvent, those exemplified in the second aspect can be used.

Further, an additive such as an antifoaming ‧ leveling agent, a thixotropic imparting agent ‧ a tackifier, a coupling agent, a dispersing agent, a flame retardant, etc. may be used as needed.

As the defoaming agent, the leveling agent, the thixotropic imparting agent, the tackifier, the coupling agent, the dispersing agent, and the flame retardant, those exemplified in the first state can be used.

The other synthetic component may, for example, be a photoacid generator such as a photoacid generator such as an azo salt, a phosphonium salt or an iodonium salt, an amine formate compound, an α-aminoketone compound or an O-indenyl ruthenium compound. Agent, barium sulfate, spheroidal vermiculite, hydrotalcite and other inorganic fillers, antimony powder, nylon powder, organic powder such as fluorine powder, radical scavenger, ultraviolet absorber, oxidation inhibitor, peroxide decomposer, dense Promoters, rust inhibitors, etc.

The printed wiring board material according to the present embodiment, which is configured as described above, can be suitably used for an interlayer insulating material of a multilayer printed wiring board, in addition to being suitable for use in a solder resist and a core material. The desired effect of this state can be obtained in the printed wiring board. Further, when the present embodiment is applied to a printed wiring board material, for example, the cellulose nanofibers may be formed into a sheet shape, and the binder component may be impregnated therewith. A method of preparing a prepreg by drying in a flaky cellulose nanofiber.

The multilayer printed wiring board of the present aspect as shown in Fig. 1 can be manufactured in the same manner as the second aspect.

[Sixth aspect of the invention]

The printed wiring board material of this embodiment may be a cellulose nanofiber (hereinafter also referred to as lignocellulose nanofiber) having a number average fiber diameter of 3 nm to 1000 nm manufactured from lignocellulose and a binder component. Such a cellulose nanofiber can be obtained as follows.

(lignocellulose nanofiber)

Lignocellulose present in nature, which has a three-dimensional network stratigraphic structure in which cellulose is firmly bound to lignin and hemicellulose. The cellulose molecules in the cell wall are not monomolecular, but are regularly aggregated and formed. Dozens of crystalline microfibers (cellulose nanofibers). Specifically, the lignocellulose used in the present state, for example, woody biomass obtained from plants such as wood or agricultural products, plants, cotton, or the like, or bacterial cellulose produced from microorganisms or the like can be obtained. In order to produce cellulose nanofibers from lignocellulose, a method of mechanically pulverizing in cooperation with a medium can be used.

As such a mechanical pulverization method, for example, a ball mill (vibrating ball mill, a rotary ball mill, a star ball mill) or a rod mill, a bead mill, a disc mill, a cutter pulverizer, a hammer mill, a turbine mill Machines, extruders, mixers (high-speed rotary airfoil mixers, homogenizers), homogenizers (high-pressure homogenizers, mechanical homogenizers, ultrasonic homogenizers). Among these, the pulverization is preferably carried out by a ball mill, a rod mill, a bead mill, a disc mill, a cutter pulverizer, an extruder or a mixer. By using these pulverization methods, cellulose nanofibers can be produced relatively easily. Further, the size unevenness of the obtained cellulose nanofibers can be made small.

The medium to be used in the pulverization step is not particularly limited, and water, a low molecular compound, a polymer compound, a fatty acid or the like can be preferably used. These may be used alone or in combination of two or more. Among these, it is preferred to use a mixed water, a low molecular compound, a polymer compound or a fatty acid as a media for pulverization.

The low molecular compound among the above may, for example, be an alcohol or an ether, a ketone, an anthraquinone, a guanamine, an amine, an aromatic, a konolin or an ionic liquid. In addition, examples of the polymer compound include alcohol-based polymers, ether-based polymers, guanamine-based polymers, amine-based polymers, and aromatic polymers. Further, examples of the fatty acid include saturated fatty acids and unsaturated fatty acids. In addition, as a low molecular compound, a polymer compound, and a fatty acid used at this time, it is preferable to use water-soluble.

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

The number average fiber diameter of the cellulose nanofibers used in this embodiment must 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 cellulose nanofiber single fiber is When the thickness is 3 nm, it is substantially impossible to manufacture less than 3 nm, and when it exceeds 1000 nm, in order to obtain the desired effect of the present invention, it is necessary to add an excessive amount to deteriorate the film formability. In addition, the average fiber diameter of the cellulose nanofibers is observed by a SEM (Scanning Electron Microscope) or a TEM (Transmission Electron Microscope), and is pulled out diagonally on the photograph. Straight lines were randomly drawn from the fibers near the line at 12 o'clock. After removing the coarsest fibers and the finest fibers, the remaining 10 points were measured and the average value was taken.

In the printed wiring board material of the present invention, the blending amount of the cellulose nanofiber is preferably 0.1 to 80% by mass, more preferably 0.2%, based on the total amount of the composition after removing the organic solvent described later. 70% by mass. When the blending amount of the cellulose nanofiber is 0.1% by mass or more, the desired effect of the present state can be favorably obtained. On the other hand, when it is 80 mass% or less, film formability can be improved.

(adhesive composition)

As the binder component used in this embodiment, the same as the second aspect can be used.

(resin containing carboxyl group)

Further, when the printed wiring board material of the present embodiment is used as an alkali-developing photosensitive resist which can be developed with an aqueous alkali solution, a carboxyl group-containing resin is preferably used as the binder component.

As the resin containing a carboxyl group, the same as the second aspect can be used.

In the printed wiring board material of this form, in addition to the cellulose nanofiber and the binder component, other conventional compounding points can be suitably blended according to the use thereof.

As another conventional compounding component, a curing catalyst, a photopolymerization initiator, a coloring agent, an organic solvent, etc. are mentioned, for example.

As such a curing catalyst, a photopolymerization initiator, a colorant, and an organic solvent, those exemplified in the second aspect can be used.

Further, an additive such as an antifoaming ‧ leveling agent, a thixotropic imparting agent ‧ a tackifier, a coupling agent, a dispersing agent, a flame retardant, etc. may be used as needed.

As the defoaming agent, the leveling agent, the thixotropic imparting agent, the tackifier, the coupling agent, the dispersing agent, and the flame retardant, those exemplified in the first state can be used.

The other synthetic component may, for example, be a photoacid generator such as a photoacid generator such as an azo salt, a phosphonium salt or an iodonium salt, an amine formate compound, an α-aminoketone compound or an O-indenyl ruthenium compound. Agent, barium sulfate, spheroidal vermiculite, hydrotalcite and other inorganic fillers, antimony powder, nylon powder, organic powder such as fluorine powder, free radical make-up agent, ultraviolet absorber, peroxide decomposer, thermal polymerization inhibitor, Adhesion promoter, rust inhibitor, etc.

The printed wiring board material according to the present embodiment, which is configured as described above, can be suitably used for an interlayer insulating material of a multilayer printed wiring board, in addition to being suitable for use in a solder resist and a core material. The desired effect of this state can be obtained in the printed wiring board. In the case where the printed wiring board material of the present embodiment is applied to a core material, for example, the cellulose nanofiber can be formed into a sheet shape, and the binder component can be contained. A method of preparing a prepreg by immersing in a flaky cellulose nanofiber and drying it.

The multilayer printed wiring board of the present aspect as shown in Fig. 1 can be manufactured in the same manner as the second aspect.

[Examples]

Hereinafter, the present invention will be described in more detail by way of examples. Also, the numbers in the following tables are all expressed as parts by mass.

[Synthesis Example 1] (varnish 1)

In a 2 liter liquid separation bottle equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen introduction tube, 900 g of diethylene glycol dimethyl ether as a solvent and t-butyl as a polymerization initiator were added. Base 2-ethylhexanoate (manufactured by Nippon Oil Co., Ltd., trade name: PERBUTYL O) 21.4 g, and heated to 90 °C. After heating, 309.9 g of methacrylic acid, 116.4 g of methyl methacrylate, and 2-hydroxyethyl methacrylate modified by lactone (manufactured by DAICEL, trade name: PLACCEL FM1) were added. 109.8 g of the bis(4-t-butylcyclohexyl)peroxydicarbonate (manufactured by Nippon Oil Co., Ltd., trade name: PERROYL TCP) of 21.4 g of a polymerization initiator was added dropwise for 3 hours. Further, this was aged for 6 hours to obtain a copolymer resin containing a carboxyl group. Still, the reactions are carried out under a nitrogen atmosphere.

Next, 3,4-epoxycyclohexylmethyl acrylate (manufactured by DAICEL) was added to the obtained carboxyl group-containing copolymer resin. Trade name: CYCLOMER A200) 363.9 g, 3.6 g of dimethylbenzylamine as a ring-opening catalyst, 1.80 g of hydroquinone monomethyl ether as a polymerization inhibitor, heated to 100 ° C, and stirred by stirring A ring-opening addition reaction of an epoxy. After 16 hours, a solution containing 53.8 mass% (nonvolatile matter) of a carboxyl group-containing resin having a acid value of 108.9 mgKOH/g and a mass average molecular weight of 25,000 was obtained.

[Synthesis Example 2] (varnish 2)

In a flask equipped with a thermometer, a stirrer, a dropping funnel, and a reflux condenser, diethylene glycol monoethyl ether acetate as a solvent and azobisisobutyronitrile as a catalyst were added in a nitrogen atmosphere. Next, this was heated to 80 ° C, and the monomer obtained by mixing methacrylic acid and methyl methacrylate at a molar ratio of 0.40:0.60 was added dropwise for 2 hours. Further, after stirring for 1 hour, the temperature was raised to 115 ° C and purified to obtain a resin solution.

After cooling the resin solution, tetrabutylammonium bromide was used as a catalyst to obtain a butyl glycidyl ether at a molar ratio of 0.40 at 95 to 105 ° C for 30 hours. The addition reaction of the carboxyl group is carried out in an equal amount and is allowed to cool.

Further, the OH group of the resin obtained above was subjected to an addition reaction of tetrahydrophthalic anhydride at a molar ratio of 0.26 at 95 to 105 ° C for 8 hours. This was taken out after cooling, and a solution containing 50% by mass (nonvolatile matter) of the following carboxyl group-containing resin, which contains a carboxyl group, was obtained. The resin content of the base resin was 78.1 mgKOH/g and the mass average molecular weight was 35,000.

[Synthesis Example 3] (varnish 3)

In a flask equipped with a thermometer, a stirrer, a dropping funnel, and a reflux condenser, 210 g of a cresol novolac type epoxy resin (made by DIC (manufactured by DIC), EPICLON N-680, epoxy equivalent = 210) was used as a solvent. 96.4 g of carbitol acetate was dissolved by heating. Next, 0.1 g of hydroquinone as a polymerization inhibitor and 2.0 g of triphenylphosphine as a reaction catalyst were added thereto. The mixture was heated to 95 to 105 ° C, and 72 g of acrylic acid was slowly dropped until the acid value became 3.0 mgKOH/g or less, and the reaction was carried out for about 16 hours. After cooling the reaction product to 80 to 90 ° C, 76.1 g of tetrahydrophthalic anhydride was added and analyzed by infrared absorption until the absorption peak of the acid anhydride (1780 cm ^-1 ) disappeared, and the reaction was carried out for about 6 hours. To the reaction solution, an aromatic solvent IPSOL #150 96.4 manufactured by K.K., Ltd. was added, and the mixture was diluted and taken out. The carboxyl group-containing photosensitive polymer solution obtained in this manner had a nonvolatile content of 65% by mass and an acid value of 78 mgKOH/g of the solid content.

[Production of Cellulose Nanofiber Dispersion]

Cellulose nanofiber (manufactured by SUGINO MACHINE, BiNFi-s 10% by mass cellulose, number average fiber diameter 80 nm) was dehydrated and filtered, and carbitol acetate was added in an amount of 10 times the weight of the filtrate, and stirred for 30 minutes. After filtering. Repeat this substitution operation 3 times, add a card with a filter weight of 10 times After the alcohol acetate was added, a 10% by mass cellulose nanofiber dispersion was prepared.

<Example 1>

*1-1) Thermosetting compound 1: EPIKOTE 828 Mitsubishi Chemical Co., Ltd.

*1-2) Thermosetting compound 2: EPIKOTE 807 Mitsubishi Chemical Co., Ltd.

*1-3) Hardening catalyst 1: 2MZ-A Shikoku Chemical Industry Co., Ltd.

*1-4) Colorant: Indigo Blue

*1-5) Organic solvent: carbitol acetate

*1-6) Photocurable compound 1: bisphenol A epoxy acrylate Mitsubishi Chemical (share) system

*1-7) Photocurable Compound 2: Trimethylolpropane Triacrylate

*1-8) Photocurable compound 3: KAYAMER PM2 Nippon Chemical Co., Ltd.

*1-9) Photocuring compound 4: LIGHT ESTER HO Co., Ltd. Chemical Co., Ltd.

*1-10) Photopolymerization initiator 1: 2-ethyl hydrazine

*1-11) Hardening Catalyst 2: Finely pulverized melamine (Nissan Chemical Co., Ltd.)

*1-12) Hardening Catalyst 3: Dicyanamide

*1-13) Photopolymerization initiator 2: IRGACURE 907 BASF

*1-14) Acrylate: dipentaerythritol tetraacrylate

*1-15) Epoxy compound: TEPIC-H (Nissan Chemical Co., Ltd.)

In the following, the following were used as the test substrate.

(Test substrate 1): A FR-4 copper-clad laminate having a size of 100 mm × 150 mm and a thickness of 1.6 mm (copper thickness: 70 μm) was used, and a pattern having a width of 1 mm, a length of 100 mm, and a space of 5 mm was produced by an etching method.

(Test substrate 2): A FR-4 copper-clad laminate having a size of 100 mm × 150 mm and a thickness of 1.6 mm (copper thickness: 18 μm) was used, and a pattern having a width of 300 μm, a length of 100 mm, and a space of 3 mm was produced by an etching method.

(Test substrate 3): size 100mm × 150mm, thickness 1.6mm The FR-4 copper-clad laminate (copper thickness: 9 μm) was used to fabricate an EPC-sized B-pattern comb-type electrode pattern by an etching method.

The components were blended according to the above table, and stirred and dispersed using a triaxial roll to prepare respective solder resist compositions. Further, the numbers in the above table indicate the parts by mass.

The composition of Examples 1-1 to 1-3 and Comparative Example 1-1 was patterned by a screen printing method using a 100 mesh polyester bias plate to cover all the lines. Printing is performed on the test substrate 1. Next, a test piece was produced by heating and hardening at 140 ° C for 30 minutes using a hot air circulation type drying oven. Further, a test piece was produced in the same manner using a 350-mesh Tetoron partial plate on the test substrate 2. Further, on the test substrate 3, a test piece was produced in such a manner as to cover the comb-shaped electrode by using a 100-mesh multi-plate.

The composition of Examples 1-4 to 1-6 and Comparative Example 1-2 was printed on the test substrate 1 in a pattern capable of covering all the lines by a screen printing method using a 100-mesh polyester partial plate. . Next, using a metal halide lamp, a cumulative amount of light of ² J/cm ² was irradiated at a wavelength of 350 nm, and hardened to prepare a test piece. Further, a test piece was produced in the same manner using a 350-mesh long plate on the test substrate 2. Further, on the test substrate 3, a test piece was produced in such a manner as to cover the comb-shaped electrode by using a 100-mesh multi-plate.

The composition of Examples 1-7 to 1-15 and Comparative Examples 1-3 to 1-5 was printed on the entire surface of the test substrate 1 by a screen printing method using a 100-mesh polyester partial plate, and a hot air circulation type was used. The drying oven was dried at 80 ° C for 30 minutes. Then, using a negative pattern which can cover all the lines, the exposure was performed using an exposure machine HMW-680G W (manufactured by ORC, Ltd.) using a printed wiring board at a cumulative light amount of 700 mJ/cm ² to 1% at 30 ° C. The sodium hydrogencarbonate aqueous solution was used as a developing solution for development by a developing machine using a printed wiring board for 60 seconds, and then thermally cured by a hot air circulating drying oven at 150 ° C for 60 minutes to prepare a test piece. Further, a test piece was produced in the same manner using a 350-mesh long plate on the test substrate 2. Further, on the test substrate 3, a test piece was produced in such a manner as to cover the comb-shaped electrode by using a 100-mesh multi-plate.

[Visual assessment]

For each test piece, a 20-times magnifying glass was used to visually evaluate the state of the coating film on the line. Since the coating film is colored, the thickness is judged by the shade of the color. The evaluation criteria are as follows. The evaluation results are shown in the table below.

(Evaluation) ○: A coating film having a sufficient thickness on the line.

△: Although the coating film having a sufficient thickness on the wire, the edge portion is thinned.

×: The coating film on the line is thin.

[heat resistance]

For each test piece, each test piece coated with rosin flux was previously flowed in a solder bath set at 260 ° C for 60 seconds, washed with propylene glycol monomethyl ether acetate, and dried. The peeling test was carried out by using Saiyan's adhesive tape to confirm the peeling of the coating film. The evaluation criteria are as follows. The evaluation results are shown in the table below.

(Evaluation) ○: There was no peeling of the film at all.

×: A peeling of the coating film occurred.

[acid resistance]

Each test piece was immersed in a 10% by volume aqueous sulfuric acid solution at 25 ° C for 60 minutes, and then washed with water to dry each test piece. Thereafter, the peeling test was carried out by using Saiyan's adhesive tape to confirm the presence or absence of peeling of the coating film. The evaluation criteria are the same as above. The evaluation results are shown in the table below.

[Electrical insulation]

For the test piece of the test substrate 3, a bias voltage of DC500V was applied between the comb electrodes, and the insulation resistance value was measured. When the value is 100 GΩ or more, the evaluation is ○; when it is less than 100 GΩ, the evaluation is ×. The results are shown in the following table.

[pencil hardness]

Using the test piece of the test substrate 3, the pencil of B to 9H after grinding was pressed at an angle of about 45° so that the tip of the core was flat, and the pencil hardness at the time of peeling off of the coating film was recorded. The results are shown in the following table.

As described above, with the solder resist composition of the present invention, the coating film having a thickened circuit thickness or the like is in a state of being thinned. It is also possible to ensure the necessary thickness, and therefore, it is possible to prevent deterioration of characteristics such as heat resistance or acid resistance. Moreover, electrical insulation or surface hardness can also be obtained, and it is confirmed that it has resistance. Flux is a sufficient feature.

<Example 2> [Evaluation of the production of sheets]

Each component was blended and stirred according to the description in Table 14 below, and dispersed by a triaxial roll to prepare each composition. The addition amount of the cellulose nanofiber and the layered niobate was 10% by mass based on the total amount of the composition after removal of the solvent. Next, this composition was printed on the entire surface of a copper foil having a thickness of 18 μm by screen printing, and cured by a hot air circulating drying oven at 140 ° C for 30 minutes. Thereafter, the copper foil was removed to prepare a sheet having a thickness of 50 μm.

[Evaluation of linear expansion coefficient]

The sheet produced as described above was cut into a length of 3 mm × 30 mm. Using TMA (Thermomechanical Analysis) "EXSTAR6000", the tensile mode, 10 mm between the chucks, and a load of 30 mN were used to raise the temperature from 5 ° C / min to 200 ° C in the nitrogen atmosphere, followed by 5 ° C. /min, cool down from 200 °C to 20 °C. Thereafter, the linear expansion coefficient was obtained from the measured values of 30 ° C to 100 ° C from 20 ° C to 200 ° C at a temperature of 5 ° C / min. The evaluation results are shown in Table 14.

*2-1) Thermosetting compound 1: EPIKOTE 828 Mitsubishi Chemical Co., Ltd.

*2-2) Thermosetting compound 2: EPIKOTE 807 Mitsubishi Chemical Co., Ltd.

*2-3) Hardening Catalyst 1: 2MZ-A Shikoku Chemical Industry Co., Ltd.

*2-4) Colorant: Indigo Blue

*2-5) Layered citrate: LUCENTITE STN Co-op Chemical

*2-6) Organic solvent: carbitol acetate

Each component was blended and stirred according to the description in Table 15 below, and dispersed by a triaxial roll to prepare each composition. The addition amount of the cellulose nanofiber and the layered niobate was 10% by mass based on the total amount of the composition after removal of the solvent. Subsequently, this composition was printed on the entire surface of a copper foil having a thickness of 18 μm by screen printing, dried in a hot air circulating drying oven at 100 ° C for 30 minutes, and then dried at 170 ° C for 60 minutes. It hardens. Thereafter, the copper foil was removed, and the linear expansion coefficient of the obtained sheet having a thickness of 50 μm was measured.

*2-7) Thermosetting compound 3: UNIDIC V-8000 (solid content 40% by mass) DIC (stock) system

*2-8) Thermosetting compound 4: DENACOL EX-830 NAGASE CHEMTEX

*2-9) Hardening Catalyst 2: Triphenylphosphine

The components were blended according to the following Table 16, and they were melt-kneaded at 180 ° C for 10 minutes and at a number of revolutions of 70 rpm using a kneading machine (Laboplastomill, manufactured by Toyo Seiki Co., Ltd.). The addition amount of the cellulose nanofiber and the layered niobate was 10% by mass based on the total amount of the composition after removal of the solvent. The obtained kneaded product was subjected to hot pressing at 190 ° C, 0.5 MPa for 3 minutes, and 20 MPa for 1 minute using a press machine (LABOPRESS P2-30T, manufactured by Toyo Seiki Co., Ltd.), and further, at 23 ° C, 0.5 MPa. It takes 1 minute to perform cooling pressing. Thereby, the linear expansion coefficient of the obtained sheet having a thickness of 50 μm was measured.

*2-10) Thermoplastic Resin 1: NOVATEC PP BC03L Japan Polypropylene Co., Ltd.

Each component was blended according to the following Table 17, and kneaded and kneaded by a kneading machine (Laboplastomill, manufactured by Toyo Seiki Co., Ltd.) at 150 ° C for 10 minutes and at a number of revolutions of 70 rpm. The addition amount of the cellulose nanofiber and the layered niobate was 10% by mass based on the total amount of the composition after removal of the solvent. The obtained kneaded product was subjected to hot pressing at 160 ° C, 0.5 MPa for 3 minutes, and 20 MPa for 1 minute using a press machine (LABOPRESS P2-30T, manufactured by Toyo Seiki Co., Ltd.), and further, at 23 ° C, 0.5 MPa. It takes 1 minute to perform cooling pressing. Thereby, the linear expansion coefficient of the obtained sheet having a thickness of 50 μm was measured.

*2-11) Thermoplastic Resin 2: NOVATEC LD LC561 Japan Polyethylene Co., Ltd.

Each component was blended and stirred according to the description in Table 18 below, and dispersed by a triaxial roll to prepare each composition. The addition amount of the cellulose nanofiber and the layered niobate was 10% by mass based on the total amount of the composition after removal of the solvent. Next, this composition was printed on the entire surface of a copper foil having a thickness of 18 μm by screen printing, and dried in a hot air circulating drying oven at 120 ° C for 10 minutes, and then dried at 250 ° C for 30 minutes. Make it harden. Thereafter, the copper foil was removed, and the linear expansion coefficient of the obtained sheet having a thickness of 50 μm was measured.

*2-12) Thermoplastic Resin 3: Sakushiru SOXR-OB varnish made by Japan Kotori Paper Co., Ltd. (solid content: 70% by mass)

Each component was blended and stirred according to the description in Table 19 below, and dispersed by a triaxial roll to prepare each composition. The addition amount of the cellulose nanofiber and the layered niobate was 10% by mass based on the total amount of the composition after removal of the solvent. Next, this composition was printed on the entire surface of a copper foil having a thickness of 18 μm by screen printing, and hardened by irradiating a cumulative amount of light of ² J/cm ² at a wavelength of 350 nm using a metal halide lamp. Thereafter, the copper foil was removed, and the linear expansion coefficient of the obtained sheet having a thickness of 50 μm was measured.

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

*2-14) Photocurable Compound 2: Trimethylolpropane Triacrylate

*2-15) Photocurable compound 3: KAYAMER PM2 Nippon Chemical Co., Ltd.

*2-16) Photocuring compound 4: LIGHT ESTER HO Co., Ltd. Chemical Co., Ltd.

*2-17) Photopolymerization initiator 1: 2-ethyl hydrazine

Each component was blended and stirred according to the following Tables 20 to 22, and dispersed by a triaxial roll to prepare each composition. The addition amount of the cellulose nanofiber and the layered niobate was 10% by mass based on the total amount of the composition after removal of the solvent. Next, this composition was printed on the entire surface of a copper foil having a thickness of 18 μm by screen printing, and dried at 80 ° C for 30 minutes using a hot air circulating drying oven. Then, using a negative pattern which can cover the edge portion of the test substrate, exposure was performed using an exposure machine HMW-680GW (manufactured by ORC, Ltd.) using a printed wiring board at a cumulative light amount of 700 mJ/cm ² to 1% at 30 ° C. The sodium hydrogencarbonate aqueous solution was used as a developing solution for development by a developing machine using a printed wiring board for 60 seconds to remove the edge portion. Next, it was thermally hardened by a hot air circulating drying oven at 150 ° C for 60 minutes. Thereafter, the copper foil was removed, and the linear expansion coefficient of the obtained sheet having a thickness of 50 μm was measured.

*2-18) Hardening Catalyst 3: Micro-crushing melamine Nissan Chemical Co., Ltd.

*2-19) Hardening Catalyst 4: Dicyanamide

*2-20) Photopolymerization initiator 2: IRGACURE 907 BASF

*2-21) Photocurable compound 5: dipentaerythritol tetraacrylate

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

As described above, it was confirmed that the linear expansion coefficient was drastically reduced by using an insulating material of the cellulose nanofiber and the layered niobate in combination.

<Example 3>

*3-1) Thermosetting compound 1: EPIKOTE 828 Mitsubishi Chemical Co., Ltd.

*3-2) Thermosetting compound 2: EPIKOTE 807 Mitsubishi Chemical Co., Ltd.

*3-3) Hardening Catalyst 1: 2MZ-A Shikoku Chemical Industry Co., Ltd.

*3-4) Colorant: Indigo Blue

*3-5) Polyoxane 1: BYK-313 (solid content 15% by mass) BYK-CHEMIE JAPAN

*3-6) Polyoxane 2: SH-8400 TORAY DOW CORNING

*3-7) Polyoxane 3: KS-66 Shin-Etsu Chemical Co., Ltd.

*3-8) Fluorine compound 1: MEGAFAC RS-75 (solid content 40% by mass) DIC (share) system

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

*3-10) Organic solvent: carbitol acetate

*3-11) Thermosetting compound 3: UNIDIC V-8000 (solid content 40% by mass) DIC (share) system

*3-12) Thermosetting compound 4: DENACOL EX-830 NAGASE CHEMTEX

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

*3-14) Thermoplastic Resin 1: NOVATEC PPBC03L Japan Polypropylene Co., Ltd.

*3-15) Thermoplastic Resin 2: NOVATEC LDLC561 Japan Polyethylene Co., Ltd.

*3-16) Thermoplastic Resin 3: Sokushiru SOXR-OB (solid content 70% by mass) varnish made by Japan Kogyo Paper Co., Ltd.

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

*3-18) Photocurable Compound 2: Trimethylolpropane Triacrylate

*3-19) Photocurable compound 3: KAYAMER PM2 Nippon Chemical Co., Ltd.

*3-20) Photocurable Compound 4: LIGHT ESTER HO Co., Ltd. Chemical Co., Ltd.

*3-21) Photocurable compound 5: dipentaerythritol tetraacrylate

*3-22) Hardening Catalyst 2: Triphenylphosphine

*3-23) Hardening Catalyst 3: Micro-crushing melamine Nissan Chemical Co., Ltd.

*3-24) Hardening Catalyst 4: Dicyanamide

*3-25) Photopolymerization initiator 1: 2-ethyl hydrazine

*3-26) Photopolymerization initiator 2: IRGACURE 907 BASF

According to the blending in the above table (except for Reference Example 3-1, Reference Example 3-2, Reference Example 3-4, Reference Example 3-5, Comparative Example 3-1, and Comparative Example 3-2), each was blended and stirred. The components were dispersed using a triaxial roll to prepare each composition. Also, the numbers in the table indicate the parts by mass.

For Reference Example 3-1, Reference Example 3-4, and Comparative Example 3-1, the components were blended and a kneading machine (Laboplastomill, Toyo Seiki Co., Ltd.) was used. The system was melted and kneaded at 180 ° C for 10 minutes and at a number of revolutions of 70 rpm. The obtained kneaded product was subjected to hot pressing at 190 ° C, 0.5 MPa for 3 minutes, and 20 MPa for 1 minute using a press machine (LABOPRESS P2-30T, manufactured by Toyo Seiki Co., Ltd.), and further, at 23 ° C, 0.5 MPa. It takes 1 minute to perform cooling pressing. Thereby, a flaky cellulose nanofiber composite molded body having a thickness of 0.5 mm and 0.05 mm was obtained.

For Reference Example 3-2, Reference Example 3-5, and Comparative Example 3-2, each component was blended and melted at 150 ° C for 10 minutes and at a number of revolutions of 70 rpm using a kneading machine (Laboplastomill, manufactured by Toyo Seiki Co., Ltd.). Mixed. The obtained kneaded product was subjected to hot pressing at 160 ° C, 0.5 MPa for 3 minutes, and 20 MPa for 1 minute using a press machine (LABOPRESS P2-30T, manufactured by Toyo Seiki Co., Ltd.), and further, at 23 ° C, 0.5 MPa. It takes 1 minute to perform cooling pressing. Thereby, a flaky cellulose nanofiber composite molded body having a thickness of 0.5 mm and 0.05 mm was obtained.

[As an evaluation of interlayer insulation materials] (production of test piece)

Fig. 2 is a view showing a method of manufacturing an evaluation substrate for an interlayer insulating material. In the figure, (a) to (e-1) are plan views, and (e-2) is a cross-sectional view of (e-1). As shown in Fig. 2, the composition of Examples 3-1 to 3-13 was printed onto the insulating layer 21b by a screen printing method to be a test substrate 21 provided with a conductor layer 21a (size 50 mm × 50 mm). The entire surface of the FR-4 copper-clad laminate (with copper pad and copper thickness of 18 μm) having a thickness of 1.6 mm is hardened by a hot air circulating drying oven at 140 ° C for 30 minutes. An insulating resin layer 22 is formed. Next, a hole (via) 23 having a diameter of 100 μm is opened on the conductor layer 21a by carbonation gas, and then the smear is removed by an aqueous potassium permanganate solution, and the entire surface is adhered to electroless copper plating, and then Electrolytic copper is plated to form a plating layer 24. Further, a wiring pattern 26 is formed by an etching method to prepare a test piece. Reference numeral 25 in the figure denotes an etching resist pattern.

The compositions of Examples 3-14, 3-22 and 3-24 were printed on the entire surface of the test substrate by screen printing using a hot air circulating drying oven at 100 ° C for 30 minutes. After drying, it was cured at 170 ° C for 60 minutes. Next, a wiring pattern was formed in the same manner as described above, thereby producing a test piece.

The flaky cellulose nanofibers formed by the reference example 3-1, the reference example 3-2, the reference example 3-4, the reference example 3-5, the comparative example 3-1, and the comparative example 3-2 are composite-formed. The body (thickness: 0.05 mm) was hot-pressed at 190 ° C and 20 MPa for 1 minute on the test substrate, and further cooled at 23 ° C and 0.5 MPa for 1 minute. Next, a wiring pattern was formed in the same manner as described above, thereby producing a test piece.

The composition of Reference Example 3-3, Reference Example 3-6, and Comparative Example 3-3 was printed on the entire surface of the test substrate by a screen printing method, and was subjected to a hot air circulation type drying furnace at 120 ° C for 10 minutes. After it was dried, it was hardened at 250 ° C for 30 minutes. Next, a wiring pattern was formed in the same manner as described above, thereby producing a test piece.

The compositions of Examples 3-15, Examples 3-20, and Examples 3-25 were printed on the entire surface of the test substrate by screen printing, and irradiated with a metal halide lamp at a wavelength of 350 nm at ² J/cm ² . The amount of light is accumulated to harden it. Next, a wiring pattern was formed in the same manner as described above, thereby producing a test piece.

The compositions of Examples 3-16 to 3-18, Examples 3-21 to 3-23, and Examples 3-26 to 3-28 were printed on the entire surface by screen printing. Drying was carried out at 80 ° C for 30 minutes using a hot air circulating drying oven. Then, using a negative pattern which can cover the edge portion of the test substrate, the exposure was performed using an exposure machine HMW-680G W (manufactured by ORC, Ltd.) using a printed wiring board at a cumulative light amount of 700 mJ/cm ² at a temperature of 30 ° C. The % sodium hydrogencarbonate aqueous solution was used as a developing solution for development by a developing machine using a printed wiring board for 60 seconds, and then the hot air circulating drying oven was performed at 150 ° C for 60 minutes to thermally harden the edge portion. Next, a wiring pattern was formed in the same manner as described above, thereby producing a test piece.

(Insulation Reliability Assessment)

A DC voltage of 50 V was applied to the electrodes of the six test pieces to carry out a placement test at 130 ° C and 85%. The insulation resistance was measured in the test cell, and the time when the insulation resistance value became one-hundredth of one hour after the start of the test was recorded. If the insulation resistance value has not decreased for more than 100 hours, the evaluation is stopped immediately. The results are shown in the following table.

[As an evaluation of the core material] (Production of cellulose nanofiber sheet)

For the cellulose nanofibers, a 0.2% by mass aqueous suspension was prepared from distilled water, and the mixture was filtered using a glass filter to form a sheet having a size of 50 mm × 50 mm and a thickness of 40 μm.

(Examples 3-29)

50 parts by mass of EPIKOTE 828 manufactured by Mitsubishi Chemical Co., Ltd., 50 parts by mass of EPIKOTE 807 manufactured by Mitsubishi Chemical Co., Ltd., 3 parts by mass of 2MZ-A manufactured by Shikoku Chemicals Co., Ltd., 2 parts by mass BYK-313, manufactured by BYK-CHEMIE JAPAN Co., Ltd., and 100 parts by mass of methyl ethyl ketone were stirred to prepare a resin solution. This was impregnated into each of the cellulose nanofiber sheets, left in an environment of 50 ° C for 12 hours, taken out, and dried at 80 ° C for 5 hours to prepare a prepreg. Overlap 10 pieces of this prepreg, more on the back of the case A copper foil having a thickness of 18 μm was placed on the surface and hardened for 3 hours using a vacuum press at a temperature of 160 ° C and a pressure of 2 MPa. Next, as shown in FIGS. 3(a) to 3(c), the both sides of the laminate 21 formed of the insulating layer 21b on which the conductor layer 21a is formed are drilled at a pitch of 5 mm by drilling. A through hole 27 having a diameter of 300 μm. Thereafter, the stain is removed with an aqueous potassium permanganate solution, and electroless copper plating treatment is performed, followed by electrolytic copper plating treatment to form via holes 28. Next, as shown in FIGS. 4(a) to 4(c), a wiring pattern 26 is formed by an etching method to obtain a test piece.

(Examples 3-30)

In addition to blending 50 parts by mass of EPIKOTE 828 manufactured by Mitsubishi Chemical Co., Ltd., 50 parts by mass of EPIKOTE 807 manufactured by Mitsubishi Chemical Co., Ltd., 3 parts by mass of 2MZ-A and 0.75 parts by weight of Shikoku Chemical Industry Co., Ltd. A test piece was obtained in the same manner as in Example 3-29 except that MEGAFAC RS-75 manufactured by DIC Co., Ltd. and 100 parts by mass of methyl ethyl ketone were added and stirred to prepare a resin solution.

(Comparative Example 3-4)

In addition to blending 50 parts by mass of EPIKOTE 828 manufactured by Mitsubishi Chemical Co., Ltd., 50 parts by mass of EPIKOTE 807 manufactured by Mitsubishi Chemical Co., Ltd., 3 parts by mass of 2MZ-A manufactured by Shikoku Chemical Industries Co., Ltd., and 100 mass A test piece was obtained in the same manner as in Example 3-29 except that the methyl ethyl ketone was added and stirred to prepare a resin solution.

(Example 3-31)

In addition to 100 parts by mass of DIC UNIDIC V-8000, 23 parts by mass of NAGASE CHEMTEX DENACOL EX-830, 1 part by mass of triphenylphosphine, and 2 parts by mass of BYK-CHEMIE JAPAN A test piece was obtained in the same manner as in Example 3-29 except that BYK-313 (100 parts) and 100 parts by mass of methyl ethyl ketone were prepared and stirred to prepare a resin solution.

(Example 3-32)

In addition to 100 parts by mass of DIC (manufactured by DIC) UNIDIC V-8000, 23 parts by mass of NAGASE CHEMTEX (DENACOL EX-830), 1 part by mass of triphenylphosphine, and 0.75 parts by mass of DIC (unit) A test piece was obtained in the same manner as in Example 3-29 except that MEGAFAC RS-75 and 100 parts by mass of methyl ethyl ketone were prepared and stirred to prepare a resin solution.

(Comparative Example 3-5)

In addition to 100 parts by mass of DIC (DU) UNIDIC V-8000, 23 parts by mass of NAGASE CHEMTEX (DENACOL EX-830), 1 part by mass of triphenylphosphine, and 100 parts by mass of methyl ethyl A test piece was obtained in the same manner as in Example 3-29 except that the base ketone was stirred to prepare a resin solution.

(Reference Example 3-7)

In addition to 100 parts by mass of Sokushiru SOXR-OB manufactured by Nippon Paper Industries Co., Ltd., 1.3 parts by mass of BYK-313 manufactured by BYK-CHEMIE JAPAN Co., Ltd., and 70 parts by mass of methyl ethyl ketone, and A test piece was obtained in the same manner as in Example 3-29 except that the resin solution was prepared by stirring.

(Reference Example 3-8)

In addition to 100 parts by mass of Sokushiru SOXR-OB manufactured by Nippon Paper Industries Co., Ltd., 0.5 parts by mass of MEGAFAC RS-75, and 70 parts by mass of methyl ethyl ketone, and stirred to prepare a resin solution, A test piece was obtained in the same manner as in Example 3-29.

(Comparative Example 3-6)

The same procedure as in Example 3-29 was carried out except that 100 parts by mass of Sokushiru SOXR-OB manufactured by Nippon Paper Industries Co., Ltd. and 70 parts by mass of methyl ethyl ketone were blended and stirred to prepare a resin solution. Audition.

(Reference Example 3-9)

A copper foil of 18 μm was placed on the front and back surfaces of the sheet-like cellulose nanofiber composite molded article (thickness: 0.05 mm) of Reference Example 3-1, and was subjected to a vacuum press at a temperature of 190 ° C and a pressure of 0.5 MPa. It is heated for 1 minute. Next, as shown in FIGS. 3(a) to 3(c), the both sides of the laminate 21 formed of the insulating layer 21b on which the conductor layer 21a is formed are drilled by drilling. A through hole 27 having a drill hole diameter of 300 μm was opened at a pitch of 5 mm. Thereafter, the stain is removed with an aqueous potassium permanganate solution, and electroless copper plating treatment is performed, followed by electrolytic copper plating treatment to form via holes 28. Next, as shown in FIGS. 4(a) to 4(c), a wiring pattern 26 is formed by an etching method to obtain a test piece.

(Reference Example 3-10)

A test piece was produced in the same manner as in Reference Example 3-9 except that the sheet of Reference Example 3-4 (thickness: 0.5 mm) was used.

(Comparative Example 3-7)

A test piece was produced in the same manner as in Reference Example 3-9 except that the sheet of Comparative Example 3-1 (thickness: 0.5 mm) was used.

(Reference Example 3-11)

A test piece was produced in the same manner as in Reference Example 3-9 except that the sheet of Reference Example 3-2 (thickness: 0.5 mm) was used.

(Reference Example 3-12)

A test piece was produced in the same manner as in Reference Example 3-9 except that the sheet of Reference Example 3-5 (thickness: 0.5 mm) was used.

(Comparative Example 3-8)

In addition to using the sheet of Comparative Example 3-2 (thickness 0.5 mm), Test pieces 3-9 were used to make test pieces in the same manner.

(Insulation Reliability Assessment)

A DC voltage of 50 V was applied to the electrodes of the six test pieces to carry out a placement test at 130 ° C and 85%. The insulation resistance was measured in the test cell, and the time when the insulation resistance value became one-hundredth of one hour after the start of the test was recorded. If the insulation resistance value has not decreased for more than 100 hours, the evaluation is stopped immediately.

As described above, the insulating material to which the cellulose nanofiber was added was confirmed to have a dramatic improvement in insulation reliability by the presence or both of the polyoxosiloxane and the fluorine compound.

<Example 4> [Production of Cellulose Fiber Dispersion]

Conifer kraft pulp (NBKP) is machined using a high pressure homogenizer In the mechanical treatment, 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 the cellulose fibers. This was dehydrated and filtered, and carbitol acetate was added in an amount of 10 times the weight of the filtrate, and after stirring for 30 minutes, it was filtered. This substitution operation was repeated three times, and carbitol acetate was added in an amount of 10 times the weight of the filtrate to prepare a 10% by mass cellulose fiber dispersion.

[assessment]

The components were blended and stirred according to the following Tables 31 and 32, and dispersed by a triaxial roll to prepare each composition. The obtained composition was printed on the entire surface of a FR-4 copper-clad laminate (copper thickness: 18 μm) having a size of 150 mm × 100 mm and a thickness of 1.6 mm by screen printing, and was heated at 140 ° C for 30 minutes using a hot air circulating drying oven. It is hardened under the conditions. The film thickness after hardening was 50 μm. Thereafter, the surface of the cured product was roughened with an aqueous potassium permanganate solution, and electroless copper plating was applied to the entire surface, followed by electrolytic copper plating to prepare an evaluation substrate. A partial cut having a width of 10 mm and a length of 100 mm was placed on the copper plating portion, and one end was peeled off and rubbed with a cooker, and the load at a time of tearing 35 mm in the vertical direction at a temperature of 50 mm/min was measured at room temperature ( Peel strength).

*4-1) Thermosetting compound 1: EPIKOTE 828 Mitsubishi Chemical Co., Ltd.

*4-2) Thermosetting compound 2: EPIKOTE 807 Mitsubishi Chemical Co., Ltd.

*4-3) Hardening Catalyst 1: 2MZ-A Shikoku Chemical Industry Co., Ltd.

*4-4) Colorant: Indigo Blue

*4-5) Organic solvent: carbitol acetate

The components were blended and stirred according to the following Tables 33 and 34, and dispersed by a triaxial roll to prepare each composition. The obtained composition was printed to a size of 150 mm × 100 mm by screen printing. The entire surface of a FR-4 copper-clad laminate (thickness: 18 μm) having a thickness of 1.6 mm was dried in a hot air circulating drying oven at 100 ° C for 30 minutes, and then allowed to stand at 170 ° C for 60 minutes. hardening. The film thickness after hardening was 50 μm. Thereafter, the surface of the cured product was roughened with an aqueous potassium permanganate solution, and electroless copper plating was applied to the entire surface, followed by electrolytic copper plating to prepare an evaluation substrate. A partial cut having a width of 10 mm and a length of 100 mm was placed on the copper plating portion, and one end was peeled off and rubbed with a cooker, and the load at a time of tearing 35 mm in the vertical direction at a temperature of 50 mm/min was measured at room temperature ( Peel strength).

*4-6) Thermosetting compound 3: UNIDIC V-8000 (solid content 40% by mass) DIC (share) system

*4-7) Thermosetting compound 4: DENACOL EX-830 NAGASE CHEMTEX

*4-8) Hardening Catalyst 2: Triphenylphosphine

The components were blended according to the following Tables 35 and 36, and kneaded and kneaded at 180 ° C for 10 minutes and at a number of revolutions of 70 rpm using a kneading machine (Laboplastomill, manufactured by Toyo Seiki Co., Ltd.). The obtained kneaded product was subjected to hot pressing at 190 ° C, 0.5 MPa for 3 minutes, and 20 MPa for 1 minute using a press machine (LABOPRESS P2-30T, manufactured by Toyo Seiki Co., Ltd.), and further, at 23 ° C, 0.5 MPa. It takes 1 minute to perform cooling pressing. Thereby, a sheet having a thickness of 50 μm was obtained. The sheet was hot pressed at 190 ° C, 20 MPa for 1 minute by hot pressing on a FR-4 copper clad laminate (copper thickness 18 μm) having a size of 150 mm × 100 mm and a thickness of 1.6 mm, and further, at 23 ° C. 0.5 MPa took 1 minute to perform cooling pressing, and a test piece was produced. Thereafter, the surface of the cured product was roughened with an aqueous potassium permanganate solution, and electroless copper plating was applied to the entire surface, followed by electrolytic copper plating to prepare an evaluation substrate. A partial cut having a width of 10 mm and a length of 100 mm was placed on the copper plating portion, and one end was peeled off and rubbed with a cooker, and the load at a time of tearing 35 mm in the vertical direction at a temperature of 50 mm/min was measured at room temperature ( Peel strength).

*4-9) Thermoplastic Resin 1: NOVATEC PP BC03L Japan Polypropylene Co., Ltd.

The components were blended according to the following Tables 37 and 38, and were kneaded and kneaded by a kneading machine (Laboplastomill, manufactured by Toyo Seiki Co., Ltd.) at 150 ° C for 10 minutes and at a number of revolutions of 70 rpm. The obtained kneaded product was subjected to hot pressing at 160 ° C, 0.5 MPa for 3 minutes, and 20 MPa for 1 minute using a press machine (LABOPRESS P2-30T, manufactured by Toyo Seiki Co., Ltd.), and further, at 23 ° C, 0.5 MPa. It takes 1 minute to perform cooling pressing. Thereby, a sheet having a thickness of 50 μm was obtained. This sheet was FR-4 copper clad laminate (copper size 150 mm × 100 mm, thickness 1.6 mm) On a thickness of 18 μm, hot pressing was performed by hot pressing at 190 ° C and 20 MPa for 1 minute, and further, cooling pressing was performed at 23 ° C and 0.5 MPa for 1 minute to prepare a test piece. Thereafter, the surface of the cured product was roughened with an aqueous potassium permanganate solution, and electroless copper plating was applied to the entire surface, followed by electrolytic copper plating to prepare an evaluation substrate. A partial cut having a width of 10 mm and a length of 100 mm was placed on the copper plating portion, and one end was peeled off and rubbed with a cooker, and the load at a time of tearing 35 mm in the vertical direction at a temperature of 50 mm/min was measured at room temperature ( Peel strength).

*4-10) Thermoplastic Resin 2: NOVATEC LDLC561 Japan Polyethylene Co., Ltd.

Blending and stirring according to the following Tables 39 and 40 Each component was dispersed using a triaxial roll to prepare each composition. The obtained composition was printed on the entire surface of a FR-4 copper-clad laminate (copper thickness: 18 μm) having a size of 150 mm × 100 mm and a thickness of 1.6 mm by screen printing, and was heated at 120 ° C for 10 minutes using a hot air circulating drying oven. After drying under the conditions, it was cured at 250 ° C for 30 minutes. The film thickness after hardening was 50 μm. Thereafter, the surface of the cured product was roughened with an aqueous potassium permanganate solution, and electroless copper plating was applied to the entire surface, followed by electrolytic copper plating to prepare an evaluation substrate. A partial cut having a width of 10 mm and a length of 100 mm was placed on the copper plating portion, and one end was peeled off and rubbed with a cooker, and the load at a time of tearing 35 mm in the vertical direction at a temperature of 50 mm/min was measured at room temperature ( Peel strength).

*4-11) Thermoplastic Resin 3: Sakushiru SOXR-OB varnish made by Japan Kodak Paper Co., Ltd. (solid content: 70% by mass)

The components were blended and stirred according to the following Tables 41 and 42 and dispersed by a triaxial roll to prepare each composition. The obtained composition was printed on the entire surface of a FR-4 copper-clad laminate (copper thickness: 18 μm) having a size of 150 mm × 100 mm and a thickness of 1.6 mm by screen printing, and irradiated with a metal halide lamp at a wavelength of 350 nm at 2 J/cm. The cumulative amount of light of ² is hardened. The film thickness after hardening was 50 μm. Thereafter, the surface of the cured product was roughened with an aqueous potassium permanganate solution, and electroless copper plating was applied to the entire surface, followed by electrolytic copper plating to prepare an evaluation substrate. A partial cut having a width of 10 mm and a length of 100 mm was placed on the copper plating portion, and one end was peeled off and rubbed with a cooker, and the load at a time of tearing 35 mm in the vertical direction at a temperature of 50 mm/min was measured at room temperature ( Peel strength).

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

*4-13) Photocurable Compound 2: Trimethylolpropane Triacrylate

*4-14) Photocurable compound 3: KAYAMER PM2 Nippon Chemical Co., Ltd.

*4-15) Photocuring compound 4: LIGHT ESTER HO Co., Ltd. Chemical Co., Ltd.

*4-16) Photopolymerization initiator 1: 2-ethyl hydrazine

Each component was blended and stirred according to the following Tables 43 to 48, and dispersed by a triaxial roll to prepare each composition. The obtained composition was printed on the entire surface of a FR-4 copper-clad laminate (copper thickness: 18 μm) having a size of 150 mm × 100 mm and a thickness of 1.6 mm by screen printing, using a hot air circulating drying oven at 80 ° C, 30 Make it dry for a minute. Then, using a negative pattern which can cover the edge portion of the test substrate, the exposure was performed using an exposure machine HMW-680G W (manufactured by ORC, Ltd.) using a printed wiring board at a cumulative light amount of 700 mJ/cm ² at a temperature of 30 ° C. The % sodium hydrogencarbonate aqueous solution was used as a developing solution for development by a developing machine using a printed wiring board for 60 seconds, and then the hot air circulating drying oven was performed at 150 ° C for 60 minutes to thermally harden the edge portion. The film thickness after hardening was 50 μm. Thereafter, the surface of the cured product was roughened with an aqueous potassium permanganate solution, and electroless copper plating was applied to the entire surface, followed by electrolytic copper plating to prepare an evaluation substrate. A partial cut having a width of 10 mm and a length of 100 mm was placed on the copper plating portion, and one end was peeled off and rubbed with a cooker, and the load at a time of tearing 35 mm in the vertical direction at a temperature of 50 mm/min was measured at room temperature ( Peel strength).

*4-17) Hardening Catalyst 3: Micro-crushing melamine Nissan Chemical Co., Ltd.

*4-18) Hardening Catalyst 4: Dicyanamide

*4-19) Photopolymerization initiator 2: IRGACURE 907 BASF

*4-20) Photocurable compound 5: dipentaerythritol tetraacrylate

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

As described above, it was confirmed that the peeling strength was drastically improved 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.

<Example 5> [Manufacture of Cellulose Nanofiber Dispersion Containing Carboxylate] (Manufacturing Example 1)

Add 5g of conifer sunburn kraft pulp (manufactured by Oji Paper Co., Ltd., moisture content 50% by mass, CANADA standard water filtration (CSF) 550ml, and main number average fiber diameter exceeding 1000nm) to 2,2,6 6-tetramethylpiperidine-N-hydrocarbyloxy (TEMPO) 79 mg (0.5 mmol) and 500 ml of an aqueous solution of 515 mg (5 mmol) of sodium bromide were stirred until the pulp was uniformly dispersed. Here, 18 ml of an aqueous solution of sodium hypochlorite with 5% effective chlorine was added, and the pH was adjusted to 10 with a 0.5 N aqueous hydrochloric acid solution to start oxidation. reaction. During the reaction, although the pH in the system was lowered, a 0.5 N aqueous sodium hydroxide solution was added successively to adjust the pH to 10. After 2 hours of reaction, the mixture was filtered through a glass filter, and the filtrate was sufficiently washed with water to obtain a reaction product.

Next, distilled water was added to the above reaction product, and an aqueous dispersion having a pulp concentration of 2% by mass was stirred and dispersed in a rotary blade mixer for 5 minutes. Since the viscosity of the agitating slurry was remarkably increased, distilled water was gradually added to a concentration of 0.2% by mass of the solid content, and the mixture was continuously stirred and dispersed by a mixer to obtain a transparent gel-like aqueous solution. This was observed by TEM, and it was confirmed that the aqueous dispersion of the cellulose nanofibers having a carboxylate having an average fiber diameter of 10 nm was used. The amount of the carboxyl group of the above aqueous dispersion was 1.25 mmol/g.

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

(Manufacturing Example 2)

In addition to using 4-dimethylamino-2,2,6,6-tetramethylpiperidine-N-hydrocarbyloxy (4-dimethylamino-TEMPO) 100 mg (0.5 mmol) instead of 2,2 In the same manner as in Production Example 1, except that the amount of 6,6-tetramethylpiperidine-N-hydrocarbyloxy (TEMPO) was 79 mg, 10% by mass of the cellulose nanofiber dispersion 2 having a carboxylate was prepared. Further, the amount of the carboxyl group of the aqueous dispersion was 1.30 mmol/g, and the number average diameter of the cellulose nanofibers having the carboxylate was 12 nm.

(Manufacturing Example 3)

In addition to using 4-carboxy-2,2,6,6-tetramethylpiperidine-N-hydrocarbyloxy (4-carboxy-TEMPO) 101 mg (0.5 mmol) to replace 2,2,6,6-tetramethyl A cellulose nanofiber dispersion 3 having a carboxylate salt of 10% by mass was produced in the same manner as in Production Example 1 except that the piperidine-N-hydrocarbyloxy group (TEMPO) was 79 mg. Further, the amount of the carboxyl group of the aqueous dispersion was 1.16 mmol/g, and the number average diameter of the cellulose nanofibers having the carboxylate was 10 nm.

[Manufacture of Cellulose Nanofiber Dispersion] (Manufacturing Example 4)

The board made of eucalyptus was pulverized using a cutter pulverizer to prepare wood powder having a square shape of about 0.2 mm. Next, the wood powder is subjected to high temperature and high pressure treatment in an aqueous solution of sodium sulfite or sodium hydroxide to remove lignin. After 50 times of distilled water was added and stirred, and mechanical pulverization was carried out for 15 times using a disc mill, distilled water was added thereto so as to be 10% by mass, and stirred to obtain cellulose nanofibers having a number average fiber diameter of 80 nm. This was dehydrated and filtered, and carbitol acetate was added in an amount of 10 times the weight of the filtrate, and after stirring for 30 minutes, it was filtered. This substitution operation was repeated three times, and 10% by weight of the carbitol acetate was added to prepare a cellulose nanofiber dispersion 1 of 10% by mass.

*5-1) Thermosetting compound 1: EPIKOTE 828 Mitsubishi Chemical Co., Ltd.

*5-2) Thermosetting compound 2: EPIKOTE 807 Mitsubishi Chemical Co., Ltd.

*5-3) Hardening catalyst 1: 2MZ-A Shikoku Chemical Industry Co., Ltd.

*5-4) Colorant: Indigo Blue

*5-5) Organic solvent: carbitol acetate

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

*5-7) Thermosetting compound 4: DENACOL EX-830 NAGASE CHEMTEX

*5-8) Hardening Catalyst 2: Triphenylphosphine

*5-9) Thermoplastic Resin 1: Sokushiru SOXR-OB varnish made by Japan Kodak Paper Co., Ltd. (solid content: 70% by mass, N-methylpyrrolidone 30% by mass)

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

*5-11) Photocurable Compound 2: Trimethylolpropane Triacrylate

*5-12) Photocurable compound 3: KAYAMER PM2 Nippon Chemical Co., Ltd.

*5-13) Photocurable Compound 4: LIGHT ESTER HO Co., Ltd. Chemical Co., Ltd.

*5-14) Photopolymerization initiator 1: 2-ethyl hydrazine

*5-15) Hardening Catalyst 3: Micro-crushing melamine Nissan Chemical Co., Ltd.

*5-16) Hardening Catalyst 4: Dicyanamide

*5-17) Photopolymerization initiator 2: IRGACURE 907 BASF system

*5-18) Photocurable compound 5: dipentaerythritol tetraacrylate

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

[Production of sheet for evaluation of burst strength and crack elongation]

Each component was blended and stirred according to the description in Table 49, and dispersed by a triaxial roll to prepare each composition. Next, this composition was printed on the entire surface of a copper foil having a thickness of 18 μm by screen printing, and cured by a hot air circulating drying oven at 140 ° C for 30 minutes. Thereafter, the copper foil was removed to prepare an evaluation sheet having a thickness of 50 μm.

Each component was blended and stirred according to the description in Table 50, and dispersed by using a triaxial roll to prepare each composition. Subsequently, this composition was printed on the entire surface of a copper foil having a thickness of 18 μm by screen printing, and dried in a hot air circulating drying oven at 100 ° C for 30 minutes, and then dried at 170 ° C for 60 minutes. Make it harden. Thereafter, the copper foil was removed to prepare an evaluation sheet having a thickness of 50 μm.

Each component was blended and stirred according to the description in Table 51, and dispersed by a triaxial roll to prepare each composition. Next, this composition was printed on the entire surface of a copper foil having a thickness of 18 μm by screen printing, and dried in a hot air circulating drying oven at 120 ° C for 10 minutes, and then dried at 250 ° C for 30 minutes. Make it harden. Thereafter, the copper foil was removed to prepare an evaluation sheet having a thickness of 50 μm.

Each component was blended and stirred according to the description in Table 52, and dispersed by using a triaxial roll to prepare each composition. Next, this composition was printed on the entire surface of a copper foil having a thickness of 18 μm by screen printing, and hardened by irradiating a cumulative amount of light of ² J/cm ² at a wavelength of 350 nm using a metal halide lamp. Thereafter, the copper foil was removed to prepare an evaluation sheet having a thickness of 50 μm.

Each component was blended and stirred according to the description in Tables 53 to 55 above, and dispersed by using a triaxial roll to prepare each composition. Next, this composition was printed on the entire surface of a copper foil having a thickness of 18 μm by screen printing, and dried at 80 ° C for 30 minutes using a hot air circulating drying oven. Then, using a negative pattern that can cover the central portion of the copper foil, the exposure was performed using an exposure machine HMW-680GW (manufactured by ORC, Ltd.) using a printed wiring board at a cumulative light amount of 700 mJ/cm ² to 1% at 30 ° C. The sodium hydrogencarbonate aqueous solution was used as a developing solution for development by a developing machine using a printed wiring board for 60 seconds to remove the edge portion of the copper foil. Subsequently, it was hardened by a hot air circulating drying oven at 150 ° C for 60 minutes. Thereafter, the copper foil was removed to prepare an evaluation sheet having a thickness of 50 μm.

[Evaluation of burst strength and rupture elongation]

According to JIS K7127, the evaluation sheet is cut into a predetermined size to prepare a test piece. The test piece was measured for tensile strength [MPa] and rupture elongation [%] at a tensile speed of 10 mm/min using a tensile tester (AG SG manufactured by Shimadzu Corporation), and then based on the following evaluation criteria. to evaluate. The results are shown in Tables 56 to 59 below. In the evaluation criteria of the fracture strength and the fracture elongation, when both of them were ○, the cured product of the test piece had high toughness, and the crack resistance was excellent.

(Evaluation criteria for burst strength)

○: 75 MPa or more

△: 50 MPa or more, less than 75 MPa

×: less than 50MPa

(Evaluation criteria for fracture elongation)

○: 6% or more

△: 4% or more, less than 6%

×: less than 4%

[Production of substrate for crack resistance evaluation]

In the production of the fracture strength and the elongation at break evaluation sheet, a FR-4 copper-clad laminate (thickness: 18 μm) having a thickness of 1.6 mm was used instead of the copper foil, and a cured product having a thickness of 20 μm was obtained, and the same procedure was carried out. The copper-clad laminate was produced as a substrate for evaluation in which a cured product was formed.

[Cracking resistance evaluation]

The evaluation substrate was subjected to a cycle of 1000 cycles at -65 ° C for 30 minutes and 150 ° C for 30 minutes, and the degree of cracking and peeling of the subsequent evaluation substrate was measured by an optical microscope ( (shares) KEYENCE system VHX-2000) to observe, based on the following evaluation criteria for evaluation. The results are shown in Tables 56 to 59 below.

(assessment basis)

○: no cracking occurred

△: Cracking occurred

×: Significant cracking occurred

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

<Example 6> [Manufacture of lignocellulosic nanofiber dispersion] (Manufacturing Example 1)

The board made of eucalyptus was pulverized using a cutter pulverizer to prepare wood powder having a square shape of about 0.2 mm. Then, the distilled water having a mass of 50 times was added to the wood powder and stirred, and mechanically pulverized by a disc mill for 15 times, and distilled water was added thereto so as to be 10% by mass, followed by stirring to obtain a number average fiber diameter of 80 nm. Cellulose nanofibers. This was dehydrated and filtered, and carbitol acetate was added in an amount of 10 times the weight of the filtrate, and after stirring for 30 minutes, it was filtered. This substitution operation was repeated three times, and 10% by weight of carbitol acetate was added to prepare a 10% by mass of lignocellulose nanofiber dispersion 1 .

(Manufacturing Example 2)

The board made of Chinese fir was pulverized using a cutting pulverizer to prepare wood powder having a square shape of about 0.2 mm. Next, add to this wood flour The distilled water having a mass of 50 times was stirred and mechanically pulverized by a disc mill for 15 times, and distilled water was added thereto so as to be 10% by mass, followed by stirring to obtain cellulose nanofibers having a number average fiber diameter of 80 nm. This was dehydrated and filtered, and carbitol acetate was added in an amount of 10 times the weight of the filtrate, and after stirring for 30 minutes, it was filtered. This substitution operation was repeated three times, and 10% by weight of carbitol acetate was added to prepare a 10% by mass of lignocellulose nanofiber dispersion 2.

[Manufacture of Comparative Cellulose Nanofiber Dispersion] (Manufacturing Example 3)

The board made of eucalyptus was pulverized using a cutter pulverizer to prepare wood powder having a square shape of about 0.2 mm. Next, the wood powder is subjected to high temperature and high pressure treatment in an aqueous solution of sodium sulfite or sodium hydroxide to remove lignin. 50 times of distilled water was added thereto and stirred, and mechanically pulverized by a disc mill for 15 times, and distilled water was added thereto in an amount of 10% by mass, followed by stirring to obtain cellulose nanofibers having a number average fiber diameter of 80 nm. . This was dehydrated and filtered, and carbitol acetate was added in an amount of 10 times the weight of the filtrate, and after stirring for 30 minutes, it was filtered. This substitution operation was repeated three times, and 10% by weight of the carbitol acetate was added to prepare a cellulose nanofiber dispersion 1 of 10% by mass.

[Modulation of printed wiring board materials]

The components were blended and stirred according to the following Table 60, Table 61, and Tables 64 to 68, and dispersed by a triaxial roll to prepare each composition. Things. However, the numbers in the following tables are expressed as parts by mass.

The components were blended according to the following table 62, and they were melt-kneaded at 180 ° C for 10 minutes and at a number of revolutions of 70 rpm using a kneading machine (Laboplastomill, manufactured by Toyo Seiki Co., Ltd.). The obtained kneaded product was subjected to hot pressing at 190 ° C, 0.5 MPa for 3 minutes, and 20 MPa for 1 minute using a press machine (LABOPRESS P2-30T, manufactured by Toyo Seiki Co., Ltd.), and further, at 23 ° C, 0.5 MPa. It takes 1 minute to perform cooling pressing. Thereby, a flaky cellulose nanofiber composite molded body having a thickness of 0.5 mm and 0.05 mm was obtained.

The components were blended according to the following table 63, and they were melt-kneaded at 150 ° C for 10 minutes and at a number of revolutions of 70 rpm using a kneading machine (Laboplastomill, manufactured by Toyo Seiki Co., Ltd.). The obtained kneaded product was subjected to hot pressing at 160 ° C, 0.5 MPa for 3 minutes, and 20 MPa for 1 minute using a press machine (LABOPRESS P2-30T, manufactured by Toyo Seiki Co., Ltd.), and further, at 23 ° C, 0.5 MPa. It takes 1 minute to perform cooling pressing. Thereby, a flaky cellulose nanofiber composite molded body having a thickness of 0.5 mm and 0.05 mm was obtained.

*6-1) Thermosetting compound 1: EPIKOTE 828 Mitsubishi Chemical Co., Ltd.

*6-2) Thermosetting compound 2: EPIKOTE 807 Mitsubishi Chemical Co., Ltd.

*6-3) Hardening catalyst 1: 2MZ-A Shikoku Chemical Industry Co., Ltd.

*6-4) Pigment: Indigo Blue

*6-5) Organic solvent: carbitol acetate

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

*6-7) Thermosetting compound 4: DENACOL EX-830 NAGASE CHEMTEX system

*6-8) Hardening Catalyst 2: Triphenylphosphine

*6-9) Thermoplastic Resin 1: NOVATEC PP BC03L Japan Polypropylene Co., Ltd.

*6-10) Thermoplastic Resin 2: NOVATEC LD LC561 Japan Polyethylene Co., Ltd.

*6-11) Thermoplastic Resin 3: Svarushiru SOXR-OB varnish made by Japan Kodori Paper Co., Ltd. (solid content: 70% by mass, N-methylpyrrolidone 30% by mass)

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

*6-13) Photocurable compound 2: Trimethylolpropane triacrylate

*6-14) Photocurable compound 3: KAYAMER PM2 Nippon Chemical Co., Ltd.

*6-15) Photocuring Compound 4: LIGHT ESTER HO Co., Ltd. Chemical (share) system

*6-16) Photopolymerization initiator 1: 2-ethyl hydrazine

*6-17) Hardening Catalyst 3: Micro-crushing melamine (Nissan Chemical Co., Ltd.)

*6-18) Hardening Catalyst 4: Dicyanamide

*6-19) Photopolymerization initiator 2: IRGACURE 907 (manufactured by BASF Corporation)

*6-20) Photocurable compound 5: dipivalaerythritol tetraacrylate

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

[As an evaluation of solder resist] (production of test substrate)

An FR-4 copper-clad laminate (having a thickness of 9 μm) of a size of 100 mm × 150 mm and a thickness of 1.6 mm was used to produce a B-picture of the IPC specification by an etching method. Type comb type electrode pattern.

On the test substrate, the composition of Examples 6-1 to 6-7 and Comparative Example 6-1 was used to cover the comb electrodes by screen printing, and the hot air circulating drying oven was used. The test piece was produced by hardening it at 140 ° C for 30 minutes.

As a withstand voltage test, a DC voltage was applied to a test piece of six sheets at a voltage increase rate of 500 V per second, and the voltage at which the voltage was broken was measured. The average of 6 pieces of 4.5kV or more was evaluated as ○, and those less than 4.5kV were evaluated as ×. As a result, the total number of Examples 6-1 to 6-6 was ○, and the whole numbers of Examples 6-7 and 6-1 were ×.

Further, as an insulation reliability test, a DC voltage of 50 V was applied to each of the six test pieces, and a placement test was performed in an environment of 130 ° C and 85% RH, and the time until the short circuit was measured. The average of 6 pieces of 200 hours or more was evaluated as ○, and those less than 200 hours were evaluated as ×. As a result, the total number of Examples 6-1 to 6-6 was ○, and the whole numbers of Examples 6-7 and 6-1 were ×.

On the test substrate, the composition of Examples 6-8 to 6-14 and Comparative Example 6-2 was used to cover the comb electrodes by screen printing, and the hot air circulating drying oven was used. After drying at 100 ° C for 30 minutes, it was cured at 170 ° C for 60 minutes to prepare a test piece.

As a withstand voltage test, a DC voltage was applied to a test piece of six sheets at a voltage increase rate of 500 V per second, and the voltage at which the voltage was broken was measured. The average of 6 pieces of 5.5kV or more was evaluated as ○, and those less than 5.5kV were evaluated as ×. result On the other hand, the total number of Examples 6-8 to 6-13 was ○, and the whole numbers of Examples 6-14 and 6-2 were ×.

Further, as an insulation reliability test, a DC voltage of 50 V was applied to each of the six test pieces, and a placement test was performed in an environment of 130 ° C and 85% RH, and the time until the short circuit was measured. The average of 6 pieces of 300 hours or more was evaluated as ○, and those less than 300 hours were evaluated as ×. As a result, the total number of Examples 6-8 to 6-13 was ○, and the whole numbers of Examples 6-14 and Comparative Examples 6-2 were ×.

The sheet of Reference Example 6-1 to Reference Example 6-12, Comparative Example 6-3 to Comparative Example 6-6 (thickness: 0.05 mm) was cut and processed so as to cover the comb-shaped electrode, and then on the test substrate. The sheet was subjected to hot pressing at 190 ° C and 20 MPa for 1 minute by hot pressing, and further subjected to cooling pressing at 23 ° C and 0.5 MPa for 1 minute to prepare a test piece.

As a withstand voltage test, a DC voltage was applied to a test piece of six sheets at a voltage increase rate of 500 V per second, and the voltage at which the voltage was broken was measured. Those who have an average of 6 sheets of 3.5 kV or more are evaluated as ○, and those who are less than 3.5 kV are evaluated as ×. As a result, the total number of Reference Examples 6-1 to 6-12 was ○, and the total number of Comparative Examples 6-3 to 6-6 was ×.

Further, as an insulation reliability test, a DC voltage of 50 V was applied to each of the six test pieces, and a placement test was performed in an environment of 130 ° C and 85% RH, and the time until the short circuit was measured. The average of 6 pieces of 250 hours or more was evaluated as ○, and those less than 250 hours were evaluated as ×. As a result, the total number of Reference Examples 6-1 to 6-12 was ○, and the total number of Comparative Examples 6-3 to 6-6 was ×.

On the test substrate, the screen printing method was used, and the composition of Reference Example 6-13 to Reference Example 6-18, Comparative Example 6-7, and 6-8 was able to cover the comb-shaped electrode to perform printing, using hot air. The circulating drying oven was dried at 120 ° C for 10 minutes, and then cured at 250 ° C for 30 minutes to prepare a test piece.

As a withstand voltage test, a DC voltage was applied to a test piece of six sheets at a voltage increase rate of 500 V per second, and the voltage at which the voltage was broken was measured. The average of 6 pieces of 5.5kV or more was evaluated as ○, and those less than 5.5kV were evaluated as ×. As a result, the total number of Reference Examples 6-13 to 6-18 was ○, and the total numbers of Comparative Examples 6-7 and 6-8 were ×.

Further, as an insulation reliability test, a DC voltage of 50 V was applied to each of the six test pieces, and a placement test was performed in an environment of 130 ° C and 85% RH, and the time until the short circuit was measured. The average of 6 pieces of 250 hours or more was evaluated as ○, and those less than 250 hours were evaluated as ×. As a result, the total number of Reference Examples 6-13 to 6-18 was ○, and the total numbers of Comparative Examples 6-7 and 6-8 were ×.

On the test substrate, a screen printing method was used, and the compositions of Examples 6-15 to 6-21 and Comparative Examples 6-9 were able to cover the comb electrodes, and then the metal halide lamps were used. The cumulative amount of light of ² J/cm ² was irradiated with a wavelength of 350 nm to harden it to prepare a test piece.

As a withstand voltage test, a DC voltage was applied to a test piece of six sheets at a voltage increase rate of 500 V per second, and the voltage at which the voltage was broken was measured. Those who have an average of 6 sheets of 3.5 kV or more are evaluated as ○, and those who are less than 3.5 kV are evaluated as ×. result In the aspect, the total number of the examples 6-15 to 6-20 is ○, and the total number of the examples 6-21 and the comparative examples 6-9 is ×.

Further, as an insulation reliability test, a DC voltage of 50 V was applied to each of the six test pieces, and a placement test was performed in an environment of 130 ° C and 85% RH, and the time until the short circuit was measured. The average of 6 pieces of 100 hours or more was evaluated as ○, and those less than 100 hours were evaluated as ×. As a result, the total number of Examples 6-15 to 6-20 was ○, and the total number of Examples 6-21 and Comparative Examples 6-9 was ×.

On the test substrate, the compositions of Examples 6-22 to 6-42 and Comparative Examples 6-10 to 6-12 were printed by a screen printing method using a 100-mesh polyester partial plate. The surface was dried at 80 ° C for 30 minutes using a hot air circulating drying oven. Then, using a negative pattern of a line covering the comb-shaped electrode, exposure was performed using an exposure machine HMW-680GW (manufactured by ORC) of a printed wiring board at a cumulative light amount of 700 mJ/cm ² to 1 at 30 ° C. The sodium hydrogencarbonate aqueous solution was used as a developing solution for development by a developing machine for 60 seconds using a printed wiring board, and then thermally cured by a hot air circulating drying oven at 150 ° C for 60 minutes to prepare a test piece.

As a withstand voltage test, a DC voltage was applied to a test piece of six sheets at a voltage increase rate of 500 V per second, and the voltage at which the voltage was broken was measured. The average of 6 pieces of 4.5kV or more was evaluated as ○, and those less than 4.5kV were evaluated as ×. As a result, the total number of Examples 6-22 to 6-34 and Examples 36 to 41 was ○, and the total number of Example 35, Example 42, Comparative Example 6-10 to Comparative Example 6-12 was × .

Moreover, as an insulation reliability test, application was performed for each of six test pieces. The DC voltage of 50V was placed in an environment of 130 ° C and 85% RH, and the time until the short circuit was measured. The average of 6 pieces of 200 hours or more was evaluated as ○, and those less than 200 hours were evaluated as ×. As a result, the total number of Examples 6-22 to 6-34 and Examples 36 to 41 was ○, and the total number of Example 35, Example 42, Comparative Example 6-10 to Comparative Example 6-12 was × .

[As an evaluation of interlayer insulation materials]

The composition of Examples 6-1 to 6-7 and Comparative Example 6-1 was printed on a FR-4 copper-clad laminate having a size of 100 mm × 150 mm and a thickness of 1.6 mm by a screen printing method (copper thickness: 9 μm) The entire surface was hardened by using a hot air circulating drying oven at 140 ° C for 30 minutes. Next, the electroless copper plating is adhered, and electrolytic copper plating is adhered thereto. Thereafter, a test piece of a comb type electrode pattern of the B pattern of the IPC standard was produced by an etching method.

As a withstand voltage test, a DC voltage was applied to a test piece of six sheets at a voltage increase rate of 500 V per second, and the voltage at which the voltage was broken was measured. The average of 6 pieces of 5.5kV or more was evaluated as ○, and those less than 5.5kV were evaluated as ×. As a result, the total number of Examples 6-1 to 6-6 was ○, and the whole numbers of Examples 6-7 and 6-1 were ×.

Further, as an insulation reliability test, a DC voltage of 50 V was applied to each of the six test pieces, and a placement test was performed in an environment of 130 ° C and 85% RH, and the time until the short circuit was measured. The average of 6 pieces of 400 hours or more was evaluated as ○, and those less than 400 hours were evaluated as ×. Result side The total number of Examples 6-1 to 6-6 was ○, and the total number of Examples 6-7 and 6-1 was ×.

The compositions of Examples 6-8 to 6-14 and Comparative Example 6-2 were printed on a FR-4 copper-clad laminate having a size of 100 mm × 150 mm and a thickness of 1.6 mm by a screen printing method (copper thickness: 9 μm) The entire surface was dried in a hot air circulating drying oven at 100 ° C for 30 minutes, and then cured at 170 ° C for 60 minutes. Next, the electroless copper plating is adhered, and electrolytic copper plating is adhered thereto. Thereafter, a test piece of a comb type electrode pattern of the B pattern of the IPC standard was produced by an etching method.

As a withstand voltage test, a DC voltage was applied to a test piece of six sheets at a voltage increase rate of 500 V per second, and the voltage at which the voltage was broken was measured. The average of 6 pieces of 6.5 kV or more was evaluated as ○, and those less than 6.5 kV were evaluated as ×. As a result, the total number of Examples 6-8 to 6-13 was ○, and the whole numbers of Examples 6-14 and Comparative Examples 6-2 were ×.

Further, as an insulation reliability test, a DC voltage of 50 V was applied to each of the six test pieces, and a placement test was performed in an environment of 130 ° C and 85% RH, and the time until the short circuit was measured. The average of 6 pieces of 500 hours or more was evaluated as ○, and those less than 500 hours were evaluated as ×. As a result, the total number of Examples 6-8 to 6-13 was ○, and the whole numbers of Examples 6-14 and Comparative Examples 6-2 were ×.

On the FR-4 copper-clad laminate (copper thickness: 9 μm) having a size of 100 mm × 150 mm and a thickness of 1.6 mm, the sheets of Reference Example 6-1 to Reference Example 6-12, Comparative Example 6-3 to Comparative Example 6-6 were used. (thickness 0.05mm) by hot pressing The hot pressing was performed at 190 ° C and 20 MPa for 1 minute, and further, cooling pressing was performed at 23 ° C and 0.5 MPa for 1 minute to prepare a test piece. Next, the electroless copper plating is adhered, and electrolytic copper plating is adhered thereto. Thereafter, a test piece of a comb type electrode pattern of the B pattern of the IPC standard was produced by an etching method.

As a withstand voltage test, a DC voltage was applied to a test piece of six sheets at a voltage increase rate of 500 V per second, and the voltage at which the voltage was broken was measured. The average of 6 pieces of 4.5kV or more was evaluated as ○, and those less than 4.5kV were evaluated as ×. As a result, the total number of Reference Examples 6-1 to 6-12 was ○, and the total number of Comparative Examples 6-3 to 6-6 was ×.

Further, as an insulation reliability test, a DC voltage of 50 V was applied to each of the six test pieces, and a placement test was performed in an environment of 130 ° C and 85% RH, and the time until the short circuit was measured. The average of 6 pieces of 400 hours or more was evaluated as ○, and those less than 400 hours were evaluated as ×. As a result, the total number of Reference Examples 6-1 to 6-12 was ○, and the total number of Comparative Examples 6-3 to 6-6 was ×.

The composition of Reference Example 6-13 to Reference Example 6-18, Comparative Example 6-7, and 6-8 was printed to an FR-4 copper-clad laminate having a size of 100 mm × 150 mm and a thickness of 1.6 mm using a screen printing method ( The entire surface of the copper thickness of 9 μm was dried in a hot air circulating drying oven at 120 ° C for 10 minutes, and then cured at 250 ° C for 30 minutes. Next, the electroless copper plating is adhered, and electrolytic copper plating is adhered thereto. Thereafter, a test piece of a comb type electrode pattern of the B pattern of the IPC standard was produced by an etching method.

As a withstand voltage test, a DC voltage was applied to a test piece of six sheets at a voltage increase rate of 500 V per second, and the voltage at which the voltage was broken was measured. Those who have an average of 6 pieces of 6kV or more are evaluated as ○, and those who are less than 6kV are evaluated as ×. As a result, the total number of Reference Examples 6-13 to 6-18 was ○, and the total numbers of Comparative Examples 6-7 and 6-8 were ×.

Further, as an insulation reliability test, a DC voltage of 50 V was applied to each of the six test pieces, and a placement test was performed in an environment of 130 ° C and 85% RH, and the time until the short circuit was measured. The average of 6 pieces of 400 hours or more was evaluated as ○, and those less than 400 hours were evaluated as ×. As a result, the total number of Reference Examples 6-13 to 6-18 was ○, and the total numbers of Comparative Examples 6-7 and 6-8 were ×.

The compositions of Examples 6-15 to 6-21 and Comparative Examples 6-9 were printed on a FR-4 copper clad laminate (copper thickness 9 μm) having a size of 100 mm × 150 mm and a thickness of 1.6 mm by screen printing. The entire surface was then hardened by irradiating a cumulative amount of light of ² J/cm ² at a wavelength of 350 nm using a metal halide lamp. Next, the electroless copper plating is adhered, and electrolytic copper plating is adhered thereto. Thereafter, a test piece of a comb type electrode pattern of the B pattern of the IPC standard was produced by an etching method.

As a withstand voltage test, a DC voltage was applied to a test piece of six sheets at a voltage increase rate of 500 V per second, and the voltage at which the voltage was broken was measured. The average of 6 pieces of 4.5kV or more was evaluated as ○, and those less than 4.5kV were evaluated as ×. As a result, the total number of Examples 6-15 to 6-20 was ○, and the total number of Examples 6-21 and Comparative Examples 6-9 was ×.

Moreover, as an insulation reliability test, application was performed for each of six test pieces. The DC voltage of 50V was placed in an environment of 130 ° C and 85% RH, and the time until the short circuit was measured. The average of 6 pieces of 250 hours or more was evaluated as ○, and those less than 250 hours were evaluated as ×. As a result, the total number of Examples 6-15 to 6-20 was ○, and the total number of Examples 6-21 and Comparative Examples 6-9 was ×.

On a FR-4 copper-clad laminate (copper thickness: 9 μm) having a size of 100 mm × 150 mm and a thickness of 1.6 mm, using a 100-mesh polyester partial plate by screen printing, Examples 6-22 to 6-42 were used. The compositions of Comparative Examples 6-10 to 6-12 were printed on the entire surface, and dried in a hot air circulating drying oven at 80 ° C for 30 minutes. Next, a transparent PET film was used instead of the negative pattern, and exposure was performed using an exposure machine HMW-680G W (manufactured by ORC) using a printed wiring board at a cumulative light amount of 700 mJ/cm ² to 1% carbonic acid at 30 ° C. The sodium hydrogen carbonate aqueous solution was developed as a developing solution by a developing machine using a printed wiring board for 60 seconds, and then thermally cured by a hot air circulating drying oven at 150 ° C for 60 minutes. Next, the electroless copper plating is adhered, and electrolytic copper plating is adhered thereto. Thereafter, a test piece of a comb type electrode pattern of the B pattern of the IPC standard was produced by an etching method.

As a withstand voltage test, a DC voltage was applied to a test piece of six sheets at a voltage increase rate of 500 V per second, and the voltage at which the voltage was broken was measured. The average of 6 pieces of 5.5kV or more was evaluated as ○, and those less than 5.5kV were evaluated as ×. As a result, the total number of Examples 6-22 to 6-34 and Examples 6-36 to 6-41 was ○, and Examples 6-35, 6-42, and 6-10 were compared. The full number of examples 6-12 is x.

Moreover, as an insulation reliability test, application was performed for each of six test pieces. The DC voltage of 50V was placed in an environment of 130 ° C and 85% RH, and the time until the short circuit was measured. The average of 6 pieces of 400 hours or more was evaluated as ○, and those less than 400 hours were evaluated as ×. As a result, the total number of Examples 6-22 to 6-34 and Examples 6-36 to 6-41 was ○, and Examples 6-35, 6-42, and 6-10 were compared. The full number of examples 6-12 is x.

[As an evaluation of the core material] (Production of lignocellulosic nanofiber sheet)

For the lignocellulosic nanofiber dispersion 1 and the lignocellulosic nanofiber dispersion 2, 0.2% by mass of a dispersion liquid was prepared using carbitol acetate, and filtered using a glass filter to prepare a size of 100 mm × 150 mm and a thickness of 40 μm. Thin slices.

(Production of cellulose nanofiber sheet)

In the cellulose nanofiber dispersion 1, a 0.2% by mass dispersion liquid was prepared from carbitol acetate, and filtered using a glass filter to prepare a sheet having a size of 100 mm × 150 mm and a thickness of 40 μm.

50 parts by mass of EPIKOTE 828 manufactured by Mitsubishi Chemical Co., Ltd., 50 parts by mass of EPIKOTE 807 manufactured by Mitsubishi Chemical Co., Ltd., 3 parts by mass of 2MZ-A manufactured by Shikoku Chemicals Co., Ltd., 100 parts by mass Methyl ethyl ketone was stirred to obtain a resin solution. This was impregnated into each of the cellulose nanofiber sheets, left in an environment of 50 ° C for 12 hours, taken out, and dried at 80 ° C for 5 hours to prepare a prepreg. Overlap 10 pieces of this prepreg, more, A copper foil having a thickness of 18 μm was placed on the back surface of the watch, and it was cured by a vacuum press at a temperature of 160 ° C and a pressure of 2 MPa for 3 hours. Thereafter, a test piece of a comb type electrode pattern of the B pattern of the IPC standard was produced by an etching method. A test piece of the lignocellulose nanofiber dispersion 1 was used as Example 6-43, and a test piece of the lignocellulose nanofiber dispersion 2 was used as Example 6-44, and the cellulose nanofiber dispersion 1 was used. As test pieces 6 to 45, a glass cloth was used instead of the cellulose nanofibers, and those produced in the same manner were used as Comparative Examples 6-13. The filling ratio of the cellulose fibers of Examples 6-43, Examples 6-44, Examples 6-45, and Comparative Examples 6-13 was 30% by mass.

As a withstand voltage test, a DC voltage was applied to a test piece of six sheets at a voltage increase rate of 500 V per second, and the voltage at which the voltage was broken was measured. The average of 6 pieces of 5.5kV or more was evaluated as ○, and those less than 5.5kV were evaluated as ×. As a result, the total number of Examples 6-43 and 6-44 was ○, and the total number of Examples 6-45 and Comparative Examples 6-13 was ×.

Further, as an insulation reliability test, a DC voltage of 50 V was applied to each of the six test pieces, and a placement test was performed in an environment of 130 ° C and 85% RH, and the time until the short circuit was measured. The average of 6 pieces of 400 hours or more was evaluated as ○, and those less than 400 hours were evaluated as ×. As a result, the total number of Examples 6-43 and 6-44 was ○, and the total number of Examples 6-45 and Comparative Examples 6-13 was ×.

UNIDIC V-8000 manufactured by DIC Co., Ltd., 23 parts by mass of DENACOL EX-830 manufactured by NAGASE CHEMTEX Co., Ltd., 1 part by mass of triphenylphosphine, and 100 parts by mass of 100 parts by mass Methyl ethyl ketone was stirred to obtain a resin solution. This was impregnated into each of the cellulose nanofiber sheets, left in an environment of 50 ° C for 12 hours, taken out, and dried at 80 ° C for 5 hours to prepare a prepreg. 10 sheets of this prepreg were placed on top of each other, and a copper foil of 18 μm was placed on the back surface of the front surface, and hardened for 3 hours using a vacuum press at a temperature of 160 ° C and a pressure of 2 MPa. Thereafter, a test piece of a comb type electrode pattern of the B pattern of the IPC standard was produced by an etching method. A test piece of the lignocellulose nanofiber dispersion 1 was used as Example 6-46, and a test piece of the lignocellulose nanofiber dispersion 2 was used as Example 6-47, and the cellulose nanofiber dispersion 1 was used. As test pieces 6 to 48, a glass cloth was used instead of the cellulose nanofibers, and those produced in the same manner were used as Comparative Examples 6-14. The filling ratio of the cellulose fibers of Examples 6-46, Examples 6-47, Examples 6-48, and Comparative Examples 6-14 was 30% by mass.

As a withstand voltage test, a DC voltage was applied to a test piece of six sheets at a voltage increase rate of 500 V per second, and the voltage at which the voltage was broken was measured. The average of 6 pieces of 6.5 kV or more was evaluated as ○, and those less than 6.5 kV were evaluated as ×. As a result, the total number of Examples 6-46 and 6-47 was ○, and the total number of Examples 6-48 and Comparative Examples 6-14 was ×.

Further, as an insulation reliability test, a DC voltage of 50 V was applied to each of the six test pieces, and a placement test was performed in an environment of 130 ° C and 85% RH, and the time until the short circuit was measured. The average of 6 pieces of 500 hours or more was evaluated as ○, and those less than 500 hours were evaluated as ×. As a result, the total number of Examples 6-46 and 6-47 was ○, and the total number of Examples 6-48 and Comparative Examples 6-14 was ×.

100 parts by mass of Sokushiru SOXR-OB manufactured by Nippon Paper Industries 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 of the cellulose nanofiber sheets, left in an environment of 50 ° C for 12 hours, taken out, and dried at 80 ° C for 5 hours to prepare a prepreg. 10 sheets of this prepreg were placed on top of each other, and a copper foil of 18 μm was placed on the back surface of the front surface, and hardened for 3 hours using a vacuum press at a temperature of 160 ° C and a pressure of 2 MPa. Thereafter, a test piece of a comb type electrode pattern of the B pattern of the IPC standard was produced by an etching method. A test piece of the lignocellulose nanofiber dispersion 1 was used as Reference Example 6-19, and a test piece of the lignocellulose nanofiber dispersion 2 was used as Reference Example 6-20, and the cellulose nanofiber dispersion 1 was used. The test piece was designated as Comparative Example 6-15, and a glass cloth was used instead of the cellulose nanofiber and produced in the same manner as Comparative Example 6-16. The filling ratio of the cellulose fibers of Reference Examples 6 to 19, Reference Examples 6 to 20, Comparative Examples 6 to 15 and Comparative Examples 6 to 16 was 30% by mass.

As a withstand voltage test, a DC voltage was applied to a test piece of six sheets at a voltage increase rate of 500 V per second, and the voltage at which the voltage was broken was measured. Those who have an average of 6 pieces of 6kV or more are evaluated as ○, and those who are less than 6kV are evaluated as ×. As a result, the total number of Reference Examples 6-19 and 6-20 was ○, and the total number of Comparative Examples 6-15 and 6-16 was ×.

Further, as an insulation reliability test, a DC voltage of 50 V was applied to each of the six test pieces, and a placement test was performed in an environment of 130 ° C and 85% RH, and the time until the short circuit was measured. The average of 6 pieces of 400 hours or more was evaluated as ○, and those less than 400 hours were evaluated as ×. As a result, the total number of Reference Examples 6-19 and 6-20 was ○, and Comparative Examples 6-15 and 6-16 The full number is ×.

18 μm copper foil was superposed on the front and back surfaces of the sheets (thickness: 0.5 mm) of Reference Example 6-1 to Reference Example 6-12, Comparative Example 6-3 to Comparative Example 6-6, and a vacuum press was used at a temperature of 190 ° C and a pressure. Heat at 0.5 MPa for 1 minute. Thereafter, a test piece of a comb type electrode pattern of the B pattern of the IPC standard was produced by an etching method.

As a withstand voltage test, a DC voltage was applied to a test piece of six sheets at a voltage increase rate of 500 V per second, and the voltage at which the voltage was broken was measured. The average of 6 pieces of 4.5kV or more was evaluated as ○, and those less than 4.5kV were evaluated as ×. As a result, the total number of Reference Examples 6-1 to 6-12 was ○, and the total number of Comparative Examples 6-3 to 6-6 was ×.

Further, as an insulation reliability test, a DC voltage of 50 V was applied to each of the six test pieces, and a placement test was performed in an environment of 130 ° C and 85% RH, and the time until the short circuit was measured. The average of 6 pieces of 400 hours or more was evaluated as ○, and those less than 400 hours were evaluated as ×. As a result, the total number of Reference Examples 6-1 to 6-12 was ○, and the total number of Comparative Examples 6-3 to 6-6 was ×.

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

Claims (10)

A solder resist composition characterized by comprising a curable resin and a number average fiber diameter of 3 nm which is a cellulose molecule having a carboxylate content at a C6 position and a carboxyl group content of 0.1 to 3 mmol/g. 1000 nm cellulose nanofibers. The solder resist composition of claim 1, wherein the curable resin is selected from the group consisting of a thermosetting resin and a photocurable resin. The solder resist composition of claim 2, wherein the curable resin contains a carboxyl group-containing resin. A solder resist composition according to claim 1, which comprises a layered niobate. The solder resist composition of claim 1, which comprises either or both of a polyoxonium compound and a fluorine compound. The solder resist composition according to claim 1, wherein the cellulose nanofiber has a number average fiber diameter of 3 nm or more and less than 1000 nm, and further includes a cellulose fiber having a number average fiber diameter of 1 μm or more. The solder resist composition of claim 1, wherein the cellulose nanofiber is made of lignocellulose. A dry film obtained by coating and drying a solder resist composition according to any one of claims 1 to 7 on a carrier film. A cured product characterized in that the solder resist composition according to any one of claims 1 to 7 is coated and dried on a substrate to obtain a dried coating film, or the solder resist composition is coated and dried on a carrier film to obtain a dried film. Membrane, then A dry film is laminated on a substrate to form a coating film, and the coating film is obtained by curing. A printed wiring board characterized by having a cured product of claim 9.