CN105122953B - Printed circuit board material and the printed circuit board for having used the material - Google Patents

Printed circuit board material and the printed circuit board for having used the material Download PDF

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Publication number
CN105122953B
CN105122953B CN201480018767.5A CN201480018767A CN105122953B CN 105122953 B CN105122953 B CN 105122953B CN 201480018767 A CN201480018767 A CN 201480018767A CN 105122953 B CN105122953 B CN 105122953B
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China
Prior art keywords
printed circuit
circuit board
fibrous
mass
cellulose
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CN201480018767.5A
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CN105122953A (en
Inventor
角谷武德
柴田大介
宇敷滋
远藤新
三轮崇夫
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Taiyo Holdings Co Ltd
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Taiyo Holdings Co Ltd
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Priority claimed from JP2013090377A external-priority patent/JP6317068B2/en
Priority claimed from JP2013097985A external-priority patent/JP6321327B2/en
Priority claimed from JP2013097983A external-priority patent/JP6317069B2/en
Priority claimed from JP2013097986A external-priority patent/JP2014220342A/en
Priority claimed from JP2013097989A external-priority patent/JP6317071B2/en
Priority claimed from JP2013097987A external-priority patent/JP6317070B2/en
Application filed by Taiyo Holdings Co Ltd filed Critical Taiyo Holdings Co Ltd
Publication of CN105122953A publication Critical patent/CN105122953A/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L97/00—Compositions of lignin-containing materials
    • C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L97/00—Compositions of lignin-containing materials
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
    • H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
    • H05K3/34—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by soldering
    • H05K3/3452—Solder masks
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C08L2205/16—Fibres; Fibrils
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0366—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement reinforced, e.g. by fibres, fabrics
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • H05K3/285—Permanent coating compositions

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The present invention provides a kind of printed circuit board material and has used the printed circuit board of the material, which is difficult to generate the stain of the metal foils such as copper upper surface, even and if generation also easily removing.A kind of printed circuit board material, it includes Binder Composition, the cellulose nano-fibrous and acrylic copolymer compounds that number average fiber diameter is 3nm~1000nm.The printed circuit board material can be suitable for solder resist and use and the interlayer dielectic of multilayer board use.A kind of printed circuit board, it uses the printed circuit board materials.

Description

Printed circuit board material and the printed circuit board for having used the material
Technical field
The present invention relates to printed circuit board material and the printed circuit board of the material is used.
Background technology
As wiring substrates such as printed circuit boards, there are following wiring substrates：Make epoxy resin isotonic be referred to as core material Enter and the metal foils such as copper are pasted on the material formed in the fibers such as glass, and the wiring substrate of circuit is formd using etching method；Into And after forming insulating layer by being coated with the insulating resin composition of insulating resin composition or lamination sheet, form electricity The wiring substrate on road；Etc..In addition, for being protected to the circuit formed or being installed electronic unit to correct position Purpose, wiring substrate outermost layer formed solder resist.Solder resist is generally exhausted using epoxy resin or acrylate etc. Edge material (for example, see patent document 1,2,3).
However, when forming circuit, laser is used in order to output the hole of interlayer conduction (via hole), but is deposited Easily the metal foils such as copper upper surface (via hole bottom) remain stain (residue) the problem of.If in order to remove the via hole bottom Stain and strengthen abatement processes, then insulating layer can be etched, therefore, it is difficult to using plating landfill via hole bottom and via hole inside (for example, see patent document 4).
In addition, for solder resist, a part is removed and after exposing circuit, using welding etc. carry out component installation or into The taking-up of row wiring.In the exposing of the circuit, in addition to the photo development using photonasty solder resist as general approach Other than method, also using by laser machining the sharp processing method removed the solder resist of desired part expose circuit.But In laser processing method, similarly, the presence of easy residual stain (residue) during hole (via hole) with outputing above-mentioned interlayer conduction The problem of (for example, see patent document 5).
Existing technical literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2006-182991 bulletins (claims etc.)
Patent document 2：Japanese Unexamined Patent Publication 2013-36042 bulletins (claims etc.)
Patent document 3：Japanese Unexamined Patent Publication 08-269172 bulletins (claims etc.)
Patent document 4：Japanese Unexamined Patent Publication 2009-200301 bulletins (claims etc.)
Patent document 5：Japanese Unexamined Patent Publication 2010-031216 bulletins (claims, [0079]~[0086] section etc.)
Invention content
The subject that the invention solves
The purpose of the present invention is to provide a kind of printed circuit board material and the printed circuit board of the material, the print are used Printed circuit board material is difficult to generate the stain of the metal foils such as copper upper surface, even and if generation also easily removing.
Solution for solving the problem
Present inventor has performed further investigation, as a result, it has been found that, by using containing cellulose nano-fibrous and acrylic acid series The substance of copolymerization can solve the above subject, have thus completed the present invention as printed circuit board material.
That is, the printed circuit board material of the present invention is characterized in that it includes Binder Composition, number average fiber diameters to be The cellulose nano-fibrous and acrylic copolymer compound of 3nm~1000nm.
In the printed circuit board material of the present invention, as above-mentioned Binder Composition, can be suitble to using thermoplastic resin and Curable resin.
The printed circuit board material of the present invention preferably comprises phyllosilicate.In addition, the printed circuit board material of the present invention Preferably comprise any one in organo-silicon compound and fluorine compounds or both.In addition, the printed circuit board material of the present invention In, it is preferred that above-mentioned cellulose nano-fibrous number average fiber diameter is 3nm less than 1000nm, the printed circuit Plate material further includes the cellulose fibre that number average fiber diameter is 1 μm or more.
In addition, in the printed circuit board material of the present invention, it is above-mentioned cellulose nano-fibrous preferably in its structure with carboxylic Hydrochlorate.In addition, in the printed circuit board material of the present invention, it is above-mentioned cellulose nano-fibrous preferably to be manufactured by lignocellulosic.
The printed circuit board material of the present invention can be suitable for layer insulation of the solder resist with multilayer board Material is used.
In addition, the printed circuit board of the present invention is characterized in that it uses the printed circuit board materials of the invention described above.
The effect of invention
According to the present invention, print is used as by using the substance for containing cellulose nano-fibrous and acrylic copolymer compound Printed circuit board material can realize following printed circuit board materials and use the printed circuit board of the material, the printed circuit Plate material is difficult to generate the stain of the metal foils such as copper upper surface, even and if generation also easily removing.
Description of the drawings
Fig. 1 is the partial section view for a configuration example for showing the multilayer board of the present invention.
Fig. 2 is the making side for the stain removability evaluation substrate for showing solder resist and interlayer dielectic in embodiment The definition graph of method.
Fig. 3 is the definition graph of the production method for the evaluation substrate for showing the interlayer dielectic in embodiment.
Fig. 4 is the definition graph of the production method for the evaluation substrate for showing the core material in embodiment.
Fig. 5 is the definition graph of the production method for the evaluation substrate for showing other core materials in embodiment.
Specific embodiment
In the following, with reference to attached drawing, detailed description of embodiments of the present invention.
The present invention printed circuit board material be characterized in that, it includes Binder Composition, number average fiber diameter for 3nm~ The cellulose nano-fibrous and acrylic copolymer compound of 1000nm.It is above-mentioned cellulose nano-fibrous to obtain as follows.
(number average fiber diameter is the cellulose nano-fibrous of 3nm~1000nm)
It is above-mentioned cellulose nano-fibrous to obtain as follows.
As cellulose nano-fibrous raw material, can use by timber or fiber crops, bamboo, silk floss, jute, gombo hemp, beet, agriculture Regenerated celulose fibres such as paper pulp, artificial silk or the cellophane that the natural plant fibres raw material such as product residual waste, cloth obtains etc., Wherein particularly preferred paper pulp.As paper pulp, plant can be made former using by chemically or mechanically or by the two sharing Expect it is pulped obtained from the chemical pulps such as sulfate pulp or sulfite cellulose, semi-chemical pulp, chemical pulp (Chemi Ground Pulp), chemical disk grinding machinery, hot disk grinding machinery, chemical heat disk grinding machinery, disk grinding machinery, ground wood pulp and With these plant fibers deinked pulp as main component, waste magazine paper slurry, secondary corrugating material slurry etc..Wherein, particularly preferably Various sulfate pulps, such as coniferous tree unbleached sulfate pulp, the coniferous tree oxygen in the strong coniferous tree source of fibre strength expose Reveal unbleached sulfate pulp, coniferous tree bleached sulfate pulp.
Above-mentioned raw material are mainly made of cellulose, hemicellulose and lignin, and the content of wherein lignin is usually 0~ 40 mass % or so, particularly 0~10 mass % or so.About these raw material, carry out if necessary lignin removing or Bleaching, so as to carry out the adjustment of lignin amount.It should be noted that the measure of content of lignin can pass through Klason methods carry out.
In the cell wall of plant, cellulosic molecule is not unimolecule, but regularly assembles and form tens of set Have crystalline microfibre (cellulose nano-fibrous), become plant basic framework material.As a result, in order to by above-mentioned Raw material manufacture is cellulose nano-fibrous, can use following methods：Mashing or pulverization process, high temperature are implemented to above-mentioned raw material High-pressure steam is handled, using processing of phosphate etc. etc., so as to unlock the fiber to nano-scale.
Among above-mentioned, mashing or pulverization process are following methods：To the direct applied force of the raw material such as above-mentioned paper pulp with machinery Mode is beaten or is crushed, and fiber is unlocked, cellulose nano-fibrous so as to obtain.More specifically, such as high pressure is utilized Homogenizer etc. carries out mechanical treatment to paper pulp etc., and solution is split into the cellulose fibre system that fibre diameter is 0.1 μm~10 μm or so Into the water slurry of the mass % of 0.1 mass %~3 or so, further it is repeated using grinder etc. and grinds or melt broken place Reason, so as to obtain fibre diameter as the cellulose nano-fibrous of 10nm~100nm or so.
It is above-mentioned to grind or melt broken grinder " the Pure Fine that handles and for example use manufactured by the machinery production of chestnut field Mill " etc. is carried out.The grinder be at the gap for making raw material by the grinder of upper and lower two panels using it is generated impact, Raw material is crushed to the stone mortar formula pulverizer of ultra micron by centrifugal force and shearing force, can be carried out at the same time shearing, be ground, particle Change, dispersion, emulsification and fibrillation.In addition, above-mentioned ground or melt broken processing and can also manufactured using Zeng Xing Industry Co., Ltd Ultra micron grater " Super mass-colloider " carry out.Super mass-colloider are to surmount simple crushing Range and can reach as melt sense degree the granulated grater of ultra micro.Super mass-colloider are by can freely adjust The ultra micron grater for the stone mortar form that the pore-free grinding stone of the upper two panels at whole interval is formed, top grinding stone are fixed, lower part mill Stone high speed rotation.The raw material for putting into feed hopper is sent by centrifugal force in the gap of upper metate, powerful by what is generated herein Compression, shearing and force of rolling friction etc. and raw material is made to grind successively, so as to carry out ultra micro granulation.
In addition, above-mentioned high-temperature high-pressure steam processing is following methods：By the way that the raw material such as above-mentioned paper pulp are exposed to height Fiber is unlocked in warm high-pressure steam, it is cellulose nano-fibrous so as to obtain.
In addition, the above-mentioned processing using phosphate etc. is following factures：By the surface phosphoric acid of the raw material such as above-mentioned paper pulp Esterification so as to weaken the binding force between cellulose fibre, makes fiber followed by refiner processing (grind or melt broken processing) It unlocks, it is cellulose nano-fibrous so as to obtain.For example, the raw material such as above-mentioned paper pulp are impregnated in containing 50 mass % ureas and 32 matter Measure % phosphoric acid solution in, between 60 DEG C make solution be fully infiltrated into cellulose fibre, after 180 DEG C heating carry out phosphorylations, After being washed, 2 hours hydrolysis process are carried out in 60 DEG C in the aqueous hydrochloric acid solution of 3 mass %, are washed again, and then it It is handled 20 minutes or so in room temperature in the aqueous sodium carbonate of 3 mass % afterwards, completes phosphorylation, utilize refiner (above-mentioned mill Broken machine etc.) by the processed material defibering, it is cellulose nano-fibrous so as to obtain.
In addition, used in the present invention it is cellulose nano-fibrous can also be chemically modified and/or physical modification and carry High functionality.Herein, it as chemical modification, can be carried out using following methods：Pass through acetalation, acetylation, cyanoethylation, ether Change, isocyanation esterification etc. and addition functional group make the nothings such as silicate or titanate by chemical reaction or sol-gal process etc. Machine object Composite is coated etc..As the method for chemical modification, for example, the cellulose for being shaped to sheet is received Rice fiber impregnation to acetic anhydride in and heat method.In addition, the method as physical modification, for example, passing through vacuum The plating such as the physical vapor depositions such as vapor deposition, ion plating, sputtering (PVD method), chemical vapor deposition (CVD method), electroless plating or plating The method of the coated metals such as method or ceramic raw material.These modifications can be in above-mentioned before processing, can also be after treatment.
Cellulose nano-fibrous number average fiber diameter used in the present invention is needed for 3nm~1000nm, preferably 3nm ~200nm, more preferably 3nm~100nm.Since the minimum diameter of cellulose nano-fibrous single fiber is 3nm, thus substantially The number average fiber diameter less than 3nm can not be manufactured, if being in addition deteriorated more than 1000nm with the dispersibility of Binder Composition.It needs It is noted that cellulose nano-fibrous number average fiber diameter is following values：Use SEM (Scanning Electron Microscope：Scanning electron microscope) or TEM (Transmission Electron Microscope：Transmission electron Microscope) etc. observed, cross in the diagonal of photo, extract 12 points of fiber positioned adjacent out at random, remove most thick For fiber with after most thin fiber, measuring at remaining 10 points, it is cellulose nano-fibrous number average fiber diameter to take its average value.
Above-mentioned cellulose nano-fibrous blend amount used in the present invention relative to composition in addition to the solvents entirety Amount is preferably the mass % of the mass % of 0.1 mass %~80, more preferably 0.2 mass %~70.Cellulose nano-fibrous mixture In the case of measuring as more than 0.1 mass %, the desired effect of the present invention can be obtained well.On the other hand, it is 80 matter In the case of measuring below %, Film making properties improve.
As above-mentioned acrylic copolymer compound, poly- (methyl) acrylate, modified poly- (methyl) propylene can be enumerated Acid esters etc., as its concrete example, can enumerate the manufacture of BYK-CHEMIE Japan Co., Ltd. BYK-350, BYK-352, BYK-354、BYK-355、BYK-356、BYK-358N、BYK-361N、BYK-380N、BYK-381、BYK-392、BYK-394、 BYK-3440、BYK-3550、BYK-SILCLEAN3700、Disperbyk-2000、Disperbyk-2001、Disperbyk- 2020th, Disperbyk-2050, Disperbyk-2070, the manufacture of nanmu this Chemical Co., Ltd. OX-880EF, OX-881, OX- 883、OX-883HF、OX-77EF、OX-710、1970、230、LF-1980、LF-1982、LF-1983、LF-1984、LF-1985、 Kyoeisha Chemical Co., Ltd. manufacture POLYFLOW No.7, POLYFLOW No.50E, POLYFLOW No.50EHF, POLYFLOW No.54N、POLYFLOW No.75、POLYFLOW No.77、POLYFLOW No.85、POLYFLOW No.85HF、POLYFLOW No.90、POLYFLOW No.90D-50、POLYFLOW No.95、POLYFLOW PW-95、 POLYFLOW No.99C etc., but it is not limited to these.They can be used alone or can also share two or more.
In addition, the blend amount of above-mentioned acrylic copolymer compound used in invention is enough for usually used ratio, For example, relative to 100 mass parts of Binder Composition, the mass parts of preferably 0.01 mass parts~20, more preferably 0.01 mass parts ~10 mass parts, the further preferably mass parts of 0.05 mass parts~3.If the blend amount of acrylic copolymer compound is very few, Then it is possible that the desired effect of the present invention can not be obtained, if excessively, a part of liquid of acrylic copolymer compound into Divide and solidfied material surface is oozed out into from solidfied material, it may occur that so-called bleeding, thus it is not preferred.
(Binder Composition)
Binder Composition used in the present invention, can suitably using thermoplastic resin and heat-curing resin or The curable resins such as light-cured resin.
As thermoplastic resin, acrylic acid, modified acroleic acid, low density polyethylene (LDPE), high density polyethylene (HDPE), second can be enumerated Alkene-vinyl acetate copolymer, polyethylene terephthalate, polypropylene, modified polypropene, polystyrene, acrylic nitrile-butadiene Diene-styrene copolymer, cellulose acetate, polyvinyl alcohol, polyvinyl chloride, gathers inclined two chloroethene at acrylonitritrile-styrene resin The general-purpose plastics such as alkene, polylactic acid class, thermoplastic polyurethane, polyacetals, makrolon, ultra-high molecular weight polyethylene, is gathered polyamide Mutual-phenenyl two acid bromide two alcohol ester, Noryl, polysulfones, polyphenylene sulfide, polyether sulfone, polyether-ether-ketone, polyarylate, polyetherimide Amine, polyamidoimide, liquid crystal polymer, polyamide 6 T, polyamide 9T, polytetrafluoroethylene (PTFE), polyvinylidene fluoride, polyester acyl are sub- The engineering plastics such as amine, thermoplastic polyimide class, olefin-based, polystyrene, Polyester, carbamate system, amide system, chlorination The thermoplastic elastomer (TPE)s such as ethylene system, hydrogenation system.
As heat-curing resin, as long as by heating the resin to cure and show electrical insulating property, such as Bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, bisphenol E-type epoxy resin, bis-phenol M can be enumerated Bisphenol-type epoxy resins, the bisphenol A novolac type rings such as type epoxy resin, bis-phenol p-type epoxy resin, bisphenol Z type epoxy resin The phenolic resin varnish type epoxy resins such as oxygen resin, phenol novolak type epoxy resin, cresol novolac epoxy, biphenyl type Epoxy resin, biphenyl aralkyl-type epoxy resin, aryl alkene type epoxy resin, four phenylol ethane type epoxy resin, naphthalene Type epoxy resin, anthracene type epoxy resin, phenoxy group type epoxy resin, dicyclopentadiene type epoxy resin, norbornene-type epoxy Resin, adamantane type epoxy resin, fluorenes type epoxy resin, glycidyl methacrylate copolymerization are epoxy resin, cyclohexyl The copolymerization epoxy resin of maleimide and glycidyl methacrylate, epoxy-modified polybutadiene rubber derivative, CTBN modified epoxies, trimethylolpropane polyglycidyl ether, phenyl -1,3- diglycidyl ethers, biphenyl -4,4 '-two Glycidol ether, 1,6 hexanediol diglycidylether, ethylene glycol or propylene glycol diglycidyl ether, D-sorbite bunching water Glycerin ether, three (2,3- glycidyl) isocyanuric acid esters, triglycidyl group three (2- ethoxys) isocyanuric acid ester, phenol novolac The novolak phenolics such as varnish gum, cresol novolac resin, bisphenol A novolac resin, unmodified first rank Phenolic resin is modified the phenol such as the resol type phenol resins such as resol through the modified oil such as tung oil, linseed oil, walnut oil It is the resins containing triazine ring such as urea formaldehyde, phenoxy resin, urea (urea) resin, melmac, unsaturated polyester resin, double Maleimide resin, diallyl phthalate resin, organic siliconresin, resin, the norborneol with benzoxazine ring Alkene system resin, cyanate ester resin, isocyanate resin, carbamate resins, benzocyclobutane olefine resin, maleimide tree Fat, bismaleimide-triazine resin, poly-azomethine resin, Thermocurable polyimides etc..
As free-radical polymerised light-cured resin, as long as it irradiates to cure and show by active energy beam Go out the resin of electrical insulating property, particularly preferably using the compound in molecule with 1 or more ethylenic bond unsaturated bond.As Compound with ethylenic bond unsaturated bond uses known usual optical polymerism oligomer and optical polymerism vinyl monomer Deng.
As optical polymerism oligomer, unsaturated polyester system oligomer, (methyl) acrylic ester oligomer can be enumerated Deng.As (methyl) acrylic ester oligomer, phenol Novolac epoxy (methyl) acrylate, cresol novolac can be enumerated Epoxies (methyl) acrylate, the carbamic acids such as novalac epoxy (methyl) acrylate, biphenol type epoxy (methyl) acrylate Ester (methyl) acrylate, epoxy amino formic acid esters (methyl) acrylate, polyester (methyl) acrylate, polyethers (methyl) third Olefin(e) acid ester, polybutadiene-modified (methyl) acrylate etc..It should be noted that in this specification, (methyl) acrylate is Refer to the term be referred to as to acrylate, methacrylate and their mixture, the performance similar about other also phase Together.
As optical polymerism vinyl monomer, can enumerate known usual substance, such as styrene, chlorostyrene, α- The styrene derivatives such as methyl styrene；The vinyl esters such as vinyl acetate, vinyl butyrate or vinyl benzoate；Vinyl The tertiary butyl ether of isobutyl ether, vinyl butyl ether, vinyl, vinyl n-amylether, vinyl isoamyl ether, vinyl n-octadecane base The vinyl ethers such as ether, vinyl cyclohexyl ether, ethylene glycol monobutyl vinyl ethers, triethylene glycol monomethyl vinyl ethers；Third Acrylamide, Methacrylamide, N- hydroxymethylacrylamides, N- hydroxymethyls Methacrylamide, N- methoxies third Acrylamide, N- ethoxymethyl acrylamides, N- butoxy methyl acrylamides etc. (methyl) acrylic amide；Triallyl is different The allyl compounds such as cyanurate, diallyl phthalate, different diallyl phthalate；(methyl) acrylic acid- 2- ethylhexyls, (methyl) lauryl acrylate, (methyl) tetrahydrofurfuryl acrylate, (methyl) isobornyl acrylate, (first Base) (methyl) acrylic acid such as phenyl acrylate, (methyl) phenoxyethyl acrylate esters；(methyl) hydroxy-ethyl acrylate, (methyl) the hydroxyalkyl acrylates classes such as (methyl) hydroxypropyl acrylate, pentaerythrite three (methyl) acrylate；(methyl) Methoxyethyl acrylate, (methyl) ethoxyethyl acrylate etc. alkoxy alkyl alkylenes glycol list (methyl) esters of acrylic acid；Second Glycol two (methyl) acrylate, butanediol two (methyl) esters of acrylic acid, neopentyl glycol two (methyl) acrylate, 1,6- oneself Glycol two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, pentaerythrite four (methyl) acrylate, two Poly- (methyl) acrylate of the alkylidene polyols such as pentaerythrite six (methyl) acrylate；Diethylene glycol two (methyl) acrylic acid Ester, triethylene glycol two (methyl) acrylate, ethoxylated trimethylolpropane triacrylate, propoxylation trihydroxy methyl third Poly- (methyl) esters of acrylic acid of the polyoxyalkylene glycols such as alkane three (methyl) acrylate；3-hydroxypivalic acid neopentyl glycol ester two Poly- (methyl) esters of acrylic acid such as (methyl) acrylate；The isocyanides ureas such as three [(methyl) acryloyl-oxyethyl] isocyanuric acid esters Poly- (methyl) esters of acrylic acid of acid esters type etc..
As the light-cured resin of cationically polymerizable, alicyclic ring epoxy compound, oxetanes can be suitably used Compound and vinyl ether compound etc..As alicyclic ring epoxy compound therein, 3,4 can be enumerated, 3 ', 4 '-diepoxy is double Bis- (3,4- epoxycyclohexyls) propane of hexamethylene, 2,2-, bis- (3,4- the epoxycyclohexyls) -1,3- hexafluoropropane of 2,2-, bis- (3,4- Epoxycyclohexyl) methane, 1- [1,1- bis- (3,4- epoxycyclohexyls)] ethylbenzene, bis- (3,4- epoxycyclohexyls) adipate esters, 3, 4- epoxycyclohexyl-methyls (3,4- epoxies) cyclohexane carboxylate, (3,4- epoxy -6- methylcyclohexyls) methyl -3 ', 4 '-ring Bis- (the 3,4- 7-oxa-bicyclo[4.1.0s carboxylic acid) esters of oxygen -6- methylcyclohexanecarboxylic acids ester, ethylene -1,2-, 7-oxa-bicyclo[4.1.0,3,4- epoxide rings Hexyl methanol, 3,4- epoxycyclohexylethyl trimethoxy silanes etc. have alicyclic ring epoxy compound of epoxy group etc..As city Product are sold, for example, Celloxide 2000, Celloxide 2021, the Celloxide of Co., Ltd. Daicel manufactures 3000、EHPE3150；The EPOMIK VG-3101 of Mitsui Chemicals, Inc's manufacture；The E-1031S of Mitsubishi chemical Co., Ltd； TETRAD-X, TETRAD-C of Mitsubishi Gas Chemical Co., Ltd's manufacture；EPB-13, EPB- of Tso Tat Co., Ltd., Japan's manufacture 27 etc..
As oxetane compound, in addition to bis- [(3- methyl -3- oxetanylmethoxies) methyl] ethers, double [(3- ethyl -3- oxetanylmethoxies) methyl] ether, bis- [(3- methyl -3- oxetanylmethoxies) first of 1,4- Base] benzene, bis- [(3- ethyl -3- oxetanylmethoxies) methyl] benzene of 1,4-, (3- methyl -3- oxetanyls) methyl Acrylate, (3- ethyl -3- oxetanyls) methacrylate, (3- methyl -3- oxetanyls) methyl Acrylate, (3- ethyl -3- oxetanyls) methylmethacylate or more officials such as their oligomer or copolymer Outside energy oxetanes class, oxetanes alcohol and novolac resin, poly- (4-Vinyl phenol), Cardo types can be enumerated The etherates of resin with hydroxyl such as bisphenols, calixarene kind, resorcinol calixarene kind or silsesquioxane, with oxygen The oxetane compounds such as the unsaturated monomer of azetidine ring and the copolymer of (methyl) alkyl acrylate.As commercially available Product, for example, Eternacoll OXBP, OXMA, OXBP, EHO, the xylylene of Ube Industries, Ltd's manufacture Dioxygen azetidine, ARON OXETANE OXT-101, OXT-201, OXT-211, OXT- of Toagosei Co., Ltd's manufacture 221st, OXT-212, OXT-610, PNOX-1009 etc..
As vinyl ether compound, isosorbite divinyl ether, oxanorbornene divinyl can be enumerated (oxirane ring, oxetanes ring, tetrahydrofuran ring etc. have the vinyl of cyclic ether group to the ring-type ether type such as ether vinyl ethers Ether)；The vinyl aryl ethers such as Vinyl phenyl ether；The alkyl vinyl ethers such as n-butyl vinyl ether, octyl vinyl ether；Hexamethylene The cycloalkyl vinyl ethers such as base vinyl ethers；Quinhydrones divinyl ether, 1,4- butanediols divinyl ether, hexamethylene divinyl The polyfunctional vinyls ethers such as ether, cyclohexanedimethanol divinyl base ether have the substitutions such as alkyl, pi-allyl at α and/or β Vinyl ether compound of base etc..As commercially available product, for example, the 2- hydroxyls of Maruzen Petrochemical Co., Ltd.'s manufacture Ethyl vinyl ether (HEVE), diethylene glycol monovinyl base ether (DEGV), 2- hydroxybutyl vinyl ethers (HBVE), triethylene glycol Divinyl ether etc..
In addition, using the printed circuit board material of the present invention as the sense of alkali developable that can be developed with alkaline aqueous solution In the case of light type solder resist use, further preferably use containing carboxy resin as Binder Composition.
(containing carboxy resin)
As containing carboxy resin, can use the photonasty with 1 or more photonasty unsaturated double-bond containing carboxy resin, , containing any one of carboxy resin, specific substance is not limited to without photonasty unsaturated double-bond.As containing carboxyl Resin especially can suitably use the resin of act set forth below.
(1) as unsaturated carboxylic acid and with unsaturated double-bond compound copolymerization obtained from containing carboxy resin, with And be modified and have adjusted molecular weight and acid value containing carboxy resin.
(2) make to contain and there is oxirane ring and ethylenic bond insatiable hunger in carboxyl (methyl) acrylic copolymer resin and 1 molecule Contain carboxy resin with photonasty obtained from the compound reaction of group.
(3) make the compound that 1 epoxy group and unsaturated double-bond are respectively provided in 1 molecule and the change with unsaturated double-bond The copolymer for closing object is reacted with unsaturated monocarboxylic acid, is made through the secondary hydroxyl that the reaction generates and saturation or unsaturated polyacid Photonasty obtained from anhydride reactant contains carboxy resin.
(4) after hydroxyl polymer-containing is made to be reacted with saturation or unsaturated multi-anhydride, make the carboxylic acid generated by the reaction Photonasty hydroxyl and carboxyl obtained from being reacted with the compound that 1 epoxy group and unsaturated double-bond are respectively provided in 1 molecule Resin.
(5) it reacts multi-functional epoxy compound and unsaturated monocarboxylic acid, makes the secondary hydroxyl generated by the reaction Photonasty obtained from part or all is reacted with multi-anhydride contains carboxy resin.
(6) make to have in multi-functional epoxy compound, 1 molecule the hydroxyl of 2 or more hydroxyls and 1 and epoxy reaction with The compound of outer reactive group, the monocarboxylic acid reaction containing unsaturated group, make obtained reaction product and multi-anhydride anti- Photoresist containing carboxyl obtained from answering.
(7) make the reaction product of the resin with phenolic hydroxyl group and epoxyalkane or cyclic carbonate and containing unsaturated group Monocarboxylic acid react, make obtained reaction product reacted with multi-anhydride obtained from photoresist containing carboxyl.
(8) make the compound in multi-functional epoxy compound, 1 molecule at least one alcoholic extract hydroxyl group and 1 phenolic hydroxyl group and Containing unsaturated group monocarboxylic acid reaction, make the alcoholic extract hydroxyl group of obtained reaction product reacted with the anhydride group of multi-anhydride and Obtained photoresist containing carboxyl.
Other than cellulose nano-fibrous, Binder Composition and acrylic copolymer compound, printing of the invention It can be according to other usual compounding ingredients of the appropriate mixture of its purposes in circuit board material.
As other usual compounding ingredients, for example, curing catalysts, Photoepolymerizationinitiater initiater, colorant, having Solvent etc..
Curing catalysts are the substances for mainly making heat-curing resin solidification in curable resin, for example, miaow Azoles, 2-methylimidazole, 2- ethyl imidazol(e)s, 2-ethyl-4-methylimidazole, 2- phenylimidazoles, 4- phenylimidazoles, 1- cyano ethyls- The imdazole derivatives such as 2- phenylimidazoles, 1- (2- cyano ethyls) -2-ethyl-4-methylimidazole；Dicyandiamide, benzyl dimethylamine, 4- (dimethylamino)-N, N- dimethyl benzyl amines, 4- methoxyl groups-N, N- dimethyl benzyl amine, 4- methyl-N, N- dimethyl benzyl amine Wait the hydrazine compounds such as amine compounds, adipic dihydrazide, sebacic dihydrazide；Phosphorus compounds such as triphenylphosphine etc..In addition, conduct Commercially available product, for example, 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (Shikoku Chem's manufacture), U-CAT3503N, U-CAT3502T, DBU, DBN, U-CATSA102, U-CAT5002 (manufacture of San-Apro Co., Ltd.) etc., can Individually or to mix two or more use.In addition, guanamines, methyl guanamines, benzoguanamine, melamine, 2 can also be equally used, 4- diamino -6- methacryloxyethyls-s-triazine, 2- vinyl -2,4- diamino-s-triazine, 2- vinyl -4,6- Diamino-s-triazine isocyanuric acid adduct, 2,4- diamino -6- methacryloxyethyls-s-triazine isocyanide urea The Striazine derivatives such as sour addition product.
In addition, Photoepolymerizationinitiater initiater is to make the cured substance of light-cured resin in curable resin, such as can lift Go out the benzoins such as benzoin, benzoin methylether, benzoin ethyl ether, benzoin iso-propylether and benzoin alkyl ethers；Acetophenone, 2, 2- dimethoxy -2- phenyl acetophenones, 2,2- diethoxy -2- phenyl acetophenones, 2,2- diethoxy -2- phenyl acetophenones, The acetophenones such as 1,1- dichloroacetophenones；2- methyl-1s-[4- (methyl mercapto) phenyl] -2- morpholinyl -1- acetone, 2- benzyls -2- Dimethylamino -1- (4- morphlinophenyls) -1- butanone, 2- (dimethylamino) -2- [(4- aminomethyl phenyls) methyl] -1- [4- (4- Quinoline base) phenyl] the amino alkylphenones class such as -1- butanone；2-methylanthraquinone, 2- ethyl hydrazine, 2- tertiary butyls anthraquinone, 1- chloroanthraquinones Wait Anthraquinones；The thiophenes such as 2,4- dimethyl thioxanthones, 2,4- diethyl thioxanthones, 2-chlorothioxanthone, 2,4- diisopropylthioxanthones Xanthones；The ketals class such as acetophenone dimethyl ketal, benzoin dimethylether；The benzophenones such as benzophenone；Or xanthone Class；(2,6- Dimethoxybenzoyls) -2,4,4- amyls phosphine oxide, the oxidation of bis- (2,4,6- trimethylbenzoyls)-phenyl The oxygen such as phosphine, 2,4,6- trimethyl benzoyl diphenyl base phosphine oxides, ethyl -2,4,6- trimethylbenzoyl phenyl phosphinates Change phosphine；Various peroxides, cyclopentadienyltitanium series initiators etc..They can with N, N- dimethyl ethyl aminobenzoates, The light of the tertiary amines such as N, N- dimethylaminobenzoic acid isopentyl ester, amyl -4- dimethylaminobenzoic acids ester, triethylamine, triethanolamine Quick dose etc. shares.These Photoepolymerizationinitiater initiaters can be used alone or in combination of two kinds or more.
As colorant, can used as coloring pigment or dyestuff etc. with color index represent known in usual coloring Agent.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 Green 7、36、3、5、20、28、Solvent Yellow 163、Pigment Yellow 24、108、193、147、199、202、110、109、139、179、185、93、94、 95、128、155、166、180、120、151、154、156、175、181、1、2、3、4、5、6、9、10、12、61、62、62：1、65、 73、74、75、97、100、104、105、111、116、167、168、169、182、183、12、13、14、16、17、55、63、81、 83、87、126、127、152、170、172、174、176、188、198、Pigment Orange 1、5、13、14、16、17、24、 34、36、38、40、43、46、49、51、61、63、64、71、73、Pigment Red 1、2、3、4、5、6、8、9、12、14、15、 16、17、21、22、23、31、32、112、114、146、147、151、170、184、187、188、193、210、245、253、258、 266、267、268、269、37、38、41、48：1、48：2、48：3、48：4、49：1、49：2、50：1、52：1、52：2、53：1、 53：2、57：1、58：4、63：1、63：2、64：1、68、171、175、176、185、208、123、149、166、178、179、190、 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、 38th, 42, Solvent Violet 13,36, Pigment Brown 23,25, Pigment Black 1,7 etc..
As organic solvent, the ketones such as methyl ethyl ketone, cyclohexanone can be enumerated；The fragrance such as toluene, dimethylbenzene, durene Race's hydro carbons；Methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, two The glycol ethers such as ethylene glycol monoethyl ether, dipropylene glycol monoethyl ether, Triethylene glycol ethyl ether；Ethyl acetate, butyl acetate, acetic acid are molten The esters such as the carboxylate of fine agent, diethylene glycol monoethyl ether acetic acid esters and above-mentioned glycol ethers；Ethyl alcohol, propyl alcohol, ethylene glycol, propylene glycol Wait alcohols；The aliphatic hydrocarbons such as octane, decane；The petroleum solvents such as petroleum ether, naphtha, hydrogenated naphtha, solvent naphtha Deng.
In addition, as needed can contain defoaming levelling agent, thixotropy conferring agents thickener, coupling agent, dispersant, The additives such as fire retardant.
As antifoaming agent levelling agent, silicone, modified silicone, mineral oil, vegetable oil, aliphatic alcohol, fat can be used The compounds such as acid, metallic soap, fatty acid amide, polyether polyols, polyoxyalkylene alkyl ether, polyoxyalkylene fatty acid esters Deng.
As thixotropy conferring agents thickener, kaolinite, smectite, montmorillonite, bentonite, talcum, cloud can be used The clay minerals such as mother, zeolite or silica particle, silica gel, amorphous inorganic particle, polyamide-based additive, modified urea system add Add agent, wax system additive etc..
As coupling agent, can use with methoxyl group, ethyoxyl, acetyl group etc. as alkoxy, with vinyl, first Base acrylic, acrylic, epoxy group, cyclic annular epoxy group, sulfydryl, amino, diamino, acid anhydrides, urea groups, sulfide, isocyanide Acid esters etc. is as reactive functional groups, such as vinylethoxysilane, vinyltrimethoxysilane, vinyl three The ethylene base system silane compounds such as ('beta '-methoxy ethyoxyl) silane, γ-methacryloxypropyl trimethoxy silane, Gamma-amino propyl trimethoxy silicane, Ν-β-(amino-ethyl) gamma-amino propyl trimethoxy silicane, N- β-(amino-ethyl) The amino system such as gamma-amino hydroxypropyl methyl dimethoxysilane, γ-ureidopropyltriethoxysilane silane compound, γ-epoxy Propoxypropyl trimethoxy silane, β-(3,4- epoxycyclohexyls) ethyl trimethoxy silane, γ-glycidoxypropyl group first The sulfydryls system such as the epoxies such as base diethoxy silane silane compound, γ mercaptopropyitrimethoxy silane silane compound, Silane coupling agents, the isopropyls three such as the phenylaminos base system silane compound such as Ν-phenyl-gamma-amino propyl trimethoxy silicane are different Bis- (double tridecyl phosphite ester) titanate esters of stearoylation titanate esters, four octyl groups, bis- (dioctylphyrophosphoric acid ester) ethoxyacetic acids Titanate esters, three lauryl benzenesulfonyl titanate esters of isopropyl, isopropyl three (dioctylphyrophosphoric acid ester) titanate esters, tetra isopropyl are double (dioctyl phosphito ester) titanate esters, four (1,1- diene propoxy methyl -1- butyl) bis- (double tridecyl) phosphorous acid acyl-oxygens Base titanate esters, bis- (dioctylphyrophosphoric acid ester) ethylene titanate esters, three caprylyl titanate esters of isopropyl, isopropyl dimethacrylate Isostearoyl titanate esters, three stearoyl diacrylate titanate esters of isopropyl, isopropyl three (dioctylphosphoric acid ester) titanate esters, isopropyl The titanate esters systems such as three cumyl phenyl titanate esters, dicumylphenyl ethoxyacetic acid titanate esters, two isostearoyl ethylene titanate esters are coupled Agent, the compound of the zirconate of unsaturation containing ethylenic bond, the compound containing new alkoxy zirconium ester, three new capryl zirconium of new alkoxy Acid esters, (dodecyl) benzenesulfonyl of new alkoxy three zirconate, (dioctyl) Zirconium phosphoester of new alkoxy three acid esters, new alcoxyl (dioctyl) pyrophosphate of base three zirconate, new alkoxy three (ethylene diamino) ethyl zirconate, (ammonia of new alkoxy three Base) phenyl zirconate, four (2,2- diene propoxy methyl) butyl, two (double tridecyl) phosphite ester zirconates, neopentyl (diallyl) oxygroup, three new trineodecanoyl zirconates, neopentyl (diallyl) oxygroup, three (dodecyl) benzene-sulfonyl zirconium Acid esters, neopentyl (diallyl) oxygroup, three (dioctyl) phosphite ester zirconates, neopentyl (diallyl) oxygroup, three (two Octyl group) pyrophosphate zirconate, neopentyl (diallyl) oxygroup, three (N- ethylenes diamino) ethyl zirconates, neopentyl (two Pi-allyl) oxygroup, three (amino) phenyl zirconates, neopentyl (diallyl) oxygroup, trimethacrylate acid zirconate, new penta Base (diallyl) oxygroup, three acrylic acid zirconates, di neo-pentyl (diallyl) oxygroup, two p-benzoyl base zirconic acids Ester, di neo-pentyl (diallyl) oxygroup, bis- (2- propionates methyl) the butyric acid zirconiums of two (3- sulfydryls) propionic acid zirconates, 2,2- (IV), the zirconates system coupling agent such as ring two [2,2- (double 2- propionates methyl) butyric acid root] pyrophosphate-O, O, diisobutyl (oil Alkenyl) the Aluminates system coupling agent such as acetoacetyl aluminate, lkyl acetoacetates acetic acid ester aluminium diisopropyl acid esters etc..
As dispersant, polybasic carboxylic acid system, naphthalenesulfonateformaldehyde formaldehyde condensation system, polyethylene glycol, polycarboxylic acid moiety can be used High molecule-type dispersant, alkyl sulfonic acid system, quaternary ammonium system, the higher alcohol epoxies such as Arrcostab system, polyether system, the polynary amine system of polyalkylene Low molecules type dispersant such as methane series, polyol ester system, alkylpolyamines system etc..
As fire retardant, can use the hydrated metals systems such as aluminium hydroxide, magnesium hydroxide, red phosphorus, ammonium phosphate, ammonium carbonate, Zinc borate, zinc stannate, molybdenum compound system, bromine compounds system, chlorine compound system, phosphate, phosphorus-containing polyol, containing phosphamidon, trimerization Cyanamide cyanurate, melamine compound, triaizine compounds, guanidine compound, silicon polymer etc..
As other compounding ingredients, the photoacid generators such as diazol, sulfonium salt, salt compounded of iodine, urethane compound can be enumerated Photobase generators, barium sulfate, spherical silicon dioxide, the hydrotalcites such as object, α-aminoketone compound, O- acyl group oxime compounds etc. are inorganic to be filled out The organic fillers such as material, Si powder, nylon powder, fluorine powder, free radical scavenger, ultra-violet absorber, peroxide decomposer, Hot polymerization inhibitor, closely sealed accelerating agent, antirust agent etc..
The printed circuit board material of the present invention of composition described above, can be with other than it can be suitable for solder resist It is suitable for the interlayer dielectic of multilayer board, this hair can be obtained in obtained printed circuit board as a result, Bright desired effect.In addition, in the case where the present invention is suitable for printed circuit board material, such as can also use following Method：By it is above-mentioned it is cellulose nano-fibrous be shaped to sheet, Binder Composition is made to penetrate into the sheet-like fiber element nanofiber simultaneously It is dry, make prepreg.
The partial section view of a configuration example of the multilayer board of the present invention is illustrated that in Fig. 1.What is illustrated is more Layer printed circuit board can for example manufacture as follows.First, through hole is formed in the core substrate 2 for being formed with conductive pattern 1.Perforation Being formed for hole can be carried out by appropriate means such as drilling or mould punching, laser.Thereafter, it is carried out using coarse agent thick Roughening is handled.In general, roughening treatment uses n-methyl-2-pyrrolidone, n,N-Dimethylformamide, methoxypropanol Waiting alkaline aqueous solutions such as organic solvents or sodium hydroxide, caustic potash etc. makes its swelling, and uses bichromate, permanganate, smelly The oxidants such as oxygen, hydrogen peroxide/sulfuric acid, nitric acid carry out.
Then, conductive pattern 3 is formed by combination of electroless plating or plating etc..Conductor layer is formed by electroless plating Process refer to following processes：After being impregnated in the absorption that catalyst is carried out in the aqueous solution comprising plating catalyst, it is impregnated in In plating liquid, coating is precipitated.(subtractive method, half add etc.) is in the conductor layer on the surface of core substrate 2 according to conventional methods Specific circuit pattern is formed, forms conductive pattern 3 in both sides as illustrated.At this point, through hole is also formed with coating layer, As a result, be electrically connected between the connecting portion 4 of the conductive pattern 3 of above-mentioned multilayer board and the connecting portion 1a of conductive pattern 1, Form through-hole 5.
Then, by appropriate methods such as silk screen print method, spray coating method, heavy curtain methods for example in coating heat-curable composition After it is made to be heating and curing, formed interlayer insulating film 6.In the case where using dry film or prepreg, it is laminated or hot plate is suppressed And it is made to be heating and curing, form interlayer insulating film 6.Then it, such as by the appropriate means such as laser is formed for by each conductor The via hole 7 being electrically connected between the connecting portion of layer forms conductive pattern 8 using the method identical with above-mentioned conductive pattern 3.In addition, Interlayer insulating film 9, via hole 10 and conductive pattern 11 are formed using identical method.Thereafter, solder mask layer is formed in outermost layer 12, so as to manufacture multilayer board.More than, the example that interlayer insulating film and conductor layer are formed on laminated substrate is carried out Explanation, but can also replace laminated substrate using single substrate or double-sided substrate.
The printed circuit board material of the present invention preferably further includes phyllosilicate.By combining mixture cellulose nanometer Fiber and phyllosilicate, so as to than mixture any one when linear expansion coefficient is greatly reduced with less blend amount.
As above-mentioned phyllosilicate, be not particularly limited, clay mineral preferably with swellability and/or cleavage fissure or Hydrotalcite-based compound and its similar compound.As these clay minerals, for example, kaolinite, dickite, pearl Clay, galapectite, antigorite, choysotile, pyrophyllite, montmorillonite, beidellite, nontronite, saponite, sauconite, silicon magnesium Stone, hectorite, tetrasilicic -mica (tetrasilicic mica), sodium taincolite, muscovite, emerylite, talcum, vermiculite, Phlogopite, holmesite, chlorite etc..These phyllosilicates can be natural goods, or synthetic.In addition, these Phyllosilicate can be used alone, and can also share two or more.
The shape of above-mentioned phyllosilicate is not particularly limited, but when phyllosilicate multiple-layer overlapped, after organising Cleavage is difficult to, thus the thickness of the phyllosilicate of organic-philicization is not preferably 1 layer of thickness (about 1nm) as far as possible.It in addition, can To be suitably 20~500, be preferably 50 as 0.01 μm~50 μm, preferably 0.05 μm~10 μm, slenderness ratio using average length ~200 phyllosilicate.
Above-mentioned phyllosilicate has the inorganic cation that can carry out ion exchange in its interlayer.It can carry out ion friendship The inorganic cation changed refers to, is present in the metal ions such as sodium, potassium, lithium on the crystal surface of phyllosilicate.These ions With the ion exchangeable with cationic substance, the various substances with cationic can be inserted by ion-exchange reactions Enter (intercalate) to the interlayer of above-mentioned phyllosilicate.
The cation exchange capacity (CEC) of above-mentioned phyllosilicate is not particularly limited, such as preferably 25meq/ 100g~200meq/100g, more preferably 50meq/100g~150meq/100g, further preferably 90meq/100g~ 130meq/100g.If the cation exchange capacity of phyllosilicate is more than 25meq/100g, sufficient amount is made by ion exchange Cationic substance be inserted into (intercalate) to the interlayer of phyllosilicate, interlayer is by fully organic-philicization.The opposing party Face, if cation exchange capacity be 200meq/100g hereinafter, if the inter-layer bonding force of phyllosilicate will not be made to become excessively firm Gu and crystalline flake is made to become difficult to remove, good dispersibility can be maintained.
As the concrete example for the phyllosilicate for meeting above-mentioned optimum condition, for example, KUNIMINE industry strain formulas SUMECTON SA of commercial firm's manufacture, KUNIPIA F, Co-op Chemical plant formula of KUNIMINE Industrial Co., Ltd manufacture The commodity such as the SOMASIF ME-100 of commercial firm's manufacture, the LUCENTITE STN of Co-op Chemical Chemical Co., Ltd. manufacture.
In addition, organic agent of phyllosilicate used in the present invention, can be used as long as general salt, From heat resistance aspect, it is preferable to use the heat decomposition temperature disclosed in Japanese Unexamined Patent Publication 2004-107541 bulletins is high Salt.
The method for containing organic-philic agent to the interlayer for making above-mentioned phyllosilicate is not particularly limited, and holds from synthetic operation Easy aspect is set out, and preferably inorganic cation is made to exchange with organic-philic agent by ion-exchange reactions to contain organic-philic agent Method.As the inorganic cation that can carry out ion exchange of above-mentioned phyllosilicate is made ion is carried out with organic-philic agent The method of exchange, is not particularly limited, and can make by known method.Specifically, the ion exchange in water, alcohol can be used In ion exchange, the ion exchange of water/alcohol in the mixed solvent the methods of.
Specifically, after making the abundant solvation of phyllosilicate with water or alcohol etc., add in organic-philic agent and stir, with parent The inorganic cation of the interlayer of organic agent displacement layer shape silicate.Thereafter, the organic-philic agent do not replaced is carried out fully clear It washes, and filters, dries.In addition it is also possible to phyllosilicate is made directly to be reacted with organic cation in organic solvent, Huo Zhe Phyllosilicate and organic-philic agent is made to heat in an extruder and be kneaded and reacted in the presence of resin etc..
The carry out situation of above-mentioned ion exchange sharp can by known method confirm.Such as can by following methods come Confirm that the inorganic cation of phyllosilicate is replaced with organic-philic agent：By the ICP luminescence analysis of filtrate come really Recognize the method for exchanged inorganic ions；Confirm the interlayer of phyllosilicate every the side expanded using X-ray analysis Method；The existing method of organic-philic agent is confirmed by the Mass lost of temperature-rise period using thermobalance；Etc..Relative to stratiform 1 equivalent of inorganic ions that can carry out ion exchange of silicate, ion exchange is preferably more than 0.05 equivalent (5 mass %), More than more preferably 0.1 equivalent (10 mass %), further preferably more than 0.5 equivalent (50 mass %).Ion exchange is preferred It is carried out in 0 DEG C~100 DEG C of temperature, more preferably the temperature range at 10 DEG C~90 DEG C carries out, further preferably 15 DEG C~80 DEG C temperature range carry out.
In addition, relative to the entire amount of composition in addition to the solvents, above-mentioned phyllosilicate used in the present invention mixes Dosage is preferably the mass % of the mass % of 0.02 mass %~48, more preferably 0.04 mass %~42.The mixture of phyllosilicate When measuring as more than 0.02 mass %, the reducing effect of linear expansion coefficient can be obtained well.On the other hand, for 48 mass % with When lower, Film making properties improve.
According to the method, mixture is cellulose nano-fibrous and phyllosilicate by combining, and passes through synergy, Ke Yiyu Mixture any one when compared to less blend amount obtain the material that linear expansion coefficient is greatly reduced.Relative in addition to the solvents The entire amount of composition, the total amount of the blend amount of the above-mentioned cellulose nano-fibrous and phyllosilicate in the present invention are preferably The mass % of the mass % of 0.1 mass %~80, more preferably 0.2 mass %~70.
In addition, the printed circuit board material of the present invention preferably comprises any one in organo-silicon compound and fluorine compounds Or both.By comprising any one in organo-silicon compound and fluorine compounds or both, being moved between the hole that can be inhibited The effect of the generation of shifting.
(organo-silicon compound)
As above-mentioned organo-silicon compound, dimethyl silicone polymer, polyalkylphenylsilox,ne, alkyl-modified can be enumerated Silicone oil, polyether modified silicon oil, polyalkylsiloxane, polymethylsilsesquioxane, polyalkylhydrogensiloxanes, poly- Alkyl alkenyl silicon Oxygen alkane, polymethylphenylsiloxane, aralkyl modified silicone oil, alkyl aralkyl modified silicon oil etc..As commercially available product, can enumerate BYK-300、BYK-302、BYK-306、BYK-307、BYK-310、BYK-313、BYK-330、BYK-331、BYK-333、BYK- 337th, BYK-341, BYK-344, BYK-370, BYK375 (manufacture above for BYK-CHEMIE Japan Co., Ltd.), KS-66, KS-69、FZ-2110、FZ-2166、FZ-2154、FZ-2120、L-720、L-7002、SH8700、L-7001、FZ-2123、 SH8400, FZ-77, FZ-2164, FZ-2203, FZ-2208 (being manufactured above for TORAY DOW CORNING Co., Ltd.), 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 (being above SHIN-ETSU HANTOTAI's Chemical Co., Ltd. manufacture).
(fluorine compounds)
As above-mentioned fluorine compounds, for example, having the fluorine system tree of perfluoroalkyl or perfluorinated alkenyl etc. in molecule Fat.As commercially available product, for example, MEGAFAC F-444, MEGAFAC F-472, MEGAFAC F-477, MEGAFAC F-552、MEGAFAC F-553、MEGAFAC F-554、MEGAFAC F-443、MEGAFAC F-470、MEGAFAC F-470、 MEGAFAC F-475、MEGAFAC F-482、MEGAFAC F-483、MEGAFAC F-489、MEGAFAC R-30、MEGAFAC RS-75 (above is Dainippon Ink Chemicals's manufacture), Eftop EF301, Eftop EF303, Eftop EF352 (are above new autumn fields Be melted into Co., Ltd.'s manufacture), Fluorad FC-430, Fluorad FC-431 (manufacture above for Sumitomo 3M Co., Ltd.), AashiGuard AG-E300D、Surflon S-382、Surflon SC-101、Surflon SC-102、Surflon SC- 103rd, Surflon SC-104, Surflon SC-105, Surflon SC-106 (manufacture above for Asahi Glass Co., Ltd), BM-1000, BM-1100 (above is Yu Business Co., Ltd's manufacture), (above is Co., Ltd.'s NEOS systems by NBX-15, FTX-218 It makes).
Relative to 100 mass parts of Binder Composition, in above-mentioned organo-silicon compound and fluorine compounds used in the present invention Any one or both blend amount be preferably the mass parts of 0.01 mass parts~20, the mass of more preferably 0.01 mass parts~10 Part, further preferably mass parts of 0.05 mass parts~3.In organo-silicon compound and fluorine compounds any one or both When blend amount is more than 0.01 mass %, the desired effect of the present invention can be obtained well.On the other hand, it is 20 mass % In the case of below, Film making properties improve.
In addition, the printed circuit board material of the present invention preferably comprises the cellulose fibre that number average fiber diameter is 1 μm or more With above-mentioned number average fiber diameter for 3nm less than the cellulose nano-fibrous of 1000nm.By combining mixture fibre diameter Different cellulose fibre, so as to realize than previous higher peel strength.
(cellulose fibre)
Above-mentioned cellulose fibre can obtain as follows.
As the raw material of cellulose fibre, can enumerate and above-mentioned cellulose nano-fibrous same raw material.
In order to manufacture cellulose fibre by above-mentioned raw material, it can use and mashing or pulverization process are implemented to above-mentioned raw material Method.
Mechanical treatment is carried out to paper pulp etc. about above-mentioned mashing or pulverization process, such as using high pressure homogenizer etc., is unlocked It is 1 μm~10 μm or so into fibre diameter, the water slurry of the mass % of 0.1 mass %~3 or so is made, so as to obtain fibre Cellulose fiber.
In addition, such as unlocking the cellulose fibre obtained by mashing or pulverization process repeatedly with grinder, so as to Fibre diameter can be obtained as the cellulose nano-fibrous of 10~100nm or so.
In addition, cellulose fibre used in the present invention cellulose nano-fibrous can be equally chemically modified with above-mentioned And/or physical modification, so as to improve functionality.
The number average fiber diameter of cellulose fibre used in the present invention cellulose nano-fibrous is equally acquired with above-mentioned Value.
The number average fiber diameter of above-mentioned cellulose fibre needs to be 1 μm or more, preferably 1 μm~50 μm, more preferably 1 μm ~20 μm.If the number average fiber diameter of cellulose fibre is less than above range, desired effect can not be obtained.
In the present invention, in above-mentioned cellulose nano-fibrous preparation process, when fiber is unlocked to nano-scale, even if Stop processing in midway and whole amount is made to be the state do not unlocked, so as to remain the cellulose of the range of above-mentioned number average fiber diameter Fiber can also obtain the cellulose fibre for meeting the optimum condition of the present invention and cellulose nano-fibrous mixture.Therefore, It is fine in addition to meeting the cellulose fiber peacekeeping of range of above-mentioned specific number average fiber diameter in the printed circuit board material of the present invention Other than the plain nanofiber of dimension, the fibre of the number average fiber diameter outside the range with above-mentioned specific number average fiber diameter can also be included Cellulose fiber.
As above-mentioned cellulose fibre, as long as meeting the condition of above-mentioned number average fiber diameter, city can be suitably used Product are sold, are not particularly limited.
It is above-mentioned cellulose nano-fibrous by combining the above-mentioned cellulose fiber peacekeeping of mixture according to the present invention, so as to reality The now previous excellent peel strength not having.Above-mentioned cellulose fibre and above-mentioned cellulose nano-fibrous quality in the present invention Than being preferably 9:1~1:9th, 8 are more preferably:2~2:8.In the range of to be somebody's turn to do, higher peel strength can be obtained.
Relative to the entire amount of composition in addition to the solvents, the above-mentioned above-mentioned cellulose of cellulose fiber peacekeeping in this case is received The total amount of the blend amount of rice fiber is preferably the mass % of the mass % of 0.5 mass %~80, more preferably 1 mass %~70.Pass through The total amount for making the above-mentioned cellulose nano-fibrous blend amount of above-mentioned cellulose fiber peacekeeping is more than 0.5 mass %, can be obtained more High peel strength, by being 80 mass % hereinafter, good Film making properties can be obtained.
In addition, the printed circuit board material of the present invention is preferably comprised in structure is with the number average fiber diameter of carboxylate 3nm~1000nm's is cellulose nano-fibrous.Thus, it is possible to obtain the excellent printed circuit board material of crack resistance.The cellulose Nanofiber can make native cellulose fibre carry out miniaturization after aoxidizing and obtain in the following manner.
(cellulose nano-fibrous with carboxylate in structure)
First, in the water that about 10~1000 times of amounts (quality criteria) are calculated as with adiabatic drying benchmark, mixer etc. is used Native cellulose fibre is disperseed, so as to prepare aqueous dispersions.As the natural of above-mentioned cellulose nano-fibrous raw material Cellulose fibre, for example, the timber slurry such as coniferous tree system paper pulp or broad leaf tree system paper pulp, straw paper pulp or bagasse Silk flosses system paper pulp, the bacteria celluloses such as the non-timbers such as paper pulp system paper pulp, gined cotton or cotton linters etc..They can be used alone, It can be by two or more appropriately combined use.Furthermore it is possible to these native cellulose fibres are implemented with the processing such as mashing to increase in advance High surface area.
Then, in above-mentioned aqueous dispersions, using N- hydrocarbon oxy compounds as oxidation catalyst, native cellulose is carried out The oxidation processes of fiber.As the N- hydrocarbon oxy compounds, such as in addition to TEMPO (2,2,6,6- tetramethyl piperidine nitrogen oxidations Object) other than, 4- carboxyls-TEMPO, 4- acetamides-TEMPO, 4- amino-TEMPO, 4- dimethylaminos-TEMPO, 4- can be used Phosphonato-TEMPO, 4- hydroxyl TEMPO, 4- oxygroup TEMPO, 4- methoxyl group TEMPO, 4- (2- acetbromamides)-TEMPO, 2- TEMPO derivatives that azaadamantane N- oxyls etc. have various functional groups at C4 etc..As these N- oxyl compounds The additive amount of object, is enough for catalytic amount, can be 0.1 in terms of adiabatic drying benchmark usually relative to native cellulose fibre The range of the mass % of quality %~10.
In the oxidation processes of above-mentioned native cellulose fibre, oxidant and co-oxidants can be shared.As oxidant, For example, halous acid, hypohalogenous acids and high hydracid and their salt, excessively hydrogen peroxide, organic acid, wherein it is preferred that time chlorine The alkali metal hypohalite such as sour sodium or sodium hypobromite.In addition, as co-oxidants, such as the alkali bromides such as sodium bromide gold can be used Belong to.The dosage of oxidant is calculated as the mass % of about 1 mass %~100 usually relative to native cellulose fibre with adiabatic drying benchmark Range, the dosage of co-oxidants is calculated as about 1 mass %~30 usually relative to native cellulose fibre with adiabatic drying benchmark The range of quality %.
In the oxidation processes of above-mentioned native cellulose fibre, from the aspect of efficient progress oxidation reaction, preferably will The pH of aqueous dispersions maintains 9~12 range.In addition, the temperature of aqueous dispersions during oxidation processes can be at 1 DEG C~50 DEG C In the range of arbitrarily set, can not also into trip temperature control and react at room temperature.It can be 1 minute as the reaction time The range of~240 minutes.It should be noted that in order to which medicament is made to infiltrate into the inside of native cellulose fibre, by more carboxylics Base imports fiber surface, and bleeding agent can also be added in aqueous dispersions.As bleeding agent, carboxylate, sulfuric ester can be enumerated The nonionic surfactants such as the anionic surfactant such as salt, sulfonate, phosphate ester salt, polyethylene glycol type, polyol type Deng.
After the oxidation processes of above-mentioned native cellulose fibre, before miniaturization is carried out, preferably into being about to aqueous dispersions In the purification process that removes of the impurity such as the unreacted oxidant that includes and various by-products.Specifically, it can for example use Oxidation-treated native cellulose fibre is repeated to the method for washing and filtering.The natural fiber obtained after purification process Cellulose fiber is usually supplied to miniaturization processing to be infiltrated with the state of suitable quantity of water, and processing can also be dried if necessary, is formed It is fibrous or powdered.
Then, the miniaturization about native cellulose processing, will be according to the native cellulose for being desired with purification process Fiber is scattered in water equal solvent, and miniaturization is carried out with the state.The solvent as decentralized medium used in miniaturization processing Generally preferable water, according to wishing that alcohols (methanol, ethyl alcohol, isopropanol, isobutanol, sec-butyl alcohol, the tert-butyl alcohol, methyl can also be used Cellosolve, ethyl cellosolve, ethylene glycol, glycerine etc.), ethers (glycol dimethyl ether, 1,4- dioxane, tetrahydrofuran etc.), Ketone (acetone, methyl ethyl ketone, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide (DMSO) etc.) etc. dissolves in The organic solvent of water can also use their mixture.The solid of native cellulose fibre in the dispersion liquid of these solvents Constituent concentration is preferably below 50 mass %.If the solid component concentration of native cellulose fibre is more than 50 mass %, disperse High energy is needed, it is thus not preferred.The miniaturization of native cellulose processing can use low pressure homogenizer, high-pressure homogeneous Machine, grinder, cutting crusher, ball mill, jet pulverizer, beater, dissociating machine, short axle extruder, twin-screw extrusion The dispersal devices such as machine, ultrasonic stirrer, home-use juice extractor mixer carry out.
Cellulose nano-fibrous solid component concentration can be had adjusted by what miniaturization was handled according to wishing to be made Suspension or drying it is powdered.Herein, in the case where suspension is made, water can be used only and be situated between as dispersion Matter can also use the mixed solvent of water and other organic solvents, the alcohols such as ethyl alcohol, surfactant, acid, alkali etc..
It is handled by the oxidation processes of above-mentioned native cellulose fibre and miniaturization, the C6 of the structural unit of cellulosic molecule The hydroxyl of position is selectively oxidized to carboxyl via aldehyde radical, can obtain content by the carboxyl for 0.1mmol/g~ The cellulose Nanowire of high crystalline that the cellulosic molecule of 3mmol/g is formed, that there is above-mentioned specific number average fiber diameter Dimension.The cellulose nano-fibrous of the high crystalline has cellulose I type crystal structure.It means that this is cellulose nano-fibrous It is that the natural cellulosic molecule with I type crystal structures is surface-oxidised simultaneously substance obtained from miniaturization.That is, to day For right cellulose fibre, multi beam, structure occur for the microfibre for being referred to as microfibre produced in its biosynthetic process Advanced solid structure has been built, by the importing of aldehyde radical caused by oxidation processes or carboxyl, has been made strong solidifying between its microfibre Poly- power (hydrogen bond between surface) is weakened, and then is handled by miniaturization, cellulose nano-fibrous so as to obtain.By adjusting oxidation The condition of processing makes the content of carboxyl increase and decrease or make change in polarity or handled by the electrostatic repulsion or miniaturization of carboxyl, It can be with the avarage fiber diameter of control fiber element nanofiber or long, the average slenderness ratio of average fiber etc..
Above-mentioned native cellulose fibre can be identified as follows for the situation of I type crystal structures：By its Wide angle X-ray diffraction figure In the diffraction peak shape that the measure of picture obtains, in 2 θ=14 °~17 °, nearby and near 2 θ=22 °~23 ° the two positions have allusion quotation The peak of type.In addition, the situation of carboxyl is imported in cellulose nano-fibrous cellulosic molecule to be confirmed as follows：It is removing completely It has gone in the sample of moisture, has existed in the In situ ATR-FTIR (ATR) and result from the absorption (1608cm of carbonyl-1Near). In the case of carboxyl (COOH), in 1730cm in said determination-1There are absorptions.
It should be noted that due to the native cellulose fibre attachment after oxidation processes or be combined with halogen atom, for except The purpose of this residual halogen atom is gone, dehalogenate processing can also be carried out.Dehalogenate processing can be by will be after oxidation processes Native cellulose fibre is impregnated into hydrogenperoxide steam generator or ozone solution and carries out.
Specifically, for example, by the native cellulose fibre after oxidation processes with bath raio 1:5~1:100 or so, preferably 1:10~1:The condition of 60 or so (mass ratioes) is impregnated in the hydrogenperoxide steam generator of a concentration of 0.1g/L~100g/L.At this time The concentration of hydrogenperoxide steam generator is preferably 1g/L~50g/L, more preferably 5g/L~20g/L.In addition, the pH of hydrogenperoxide steam generator Preferably 8~11,9.5~10.7 are more preferably.
It should be noted that relative to the carboxylic in the cellulose of cellulose nano-fibrous weight included in aqueous dispersions The amount [mmol/g] of base can be evaluated by the following method.That is, prepare the fiber of advance accurate weighing dry weight The mass % aqueous dispersions 60ml of 0.5 mass % of plain nanofiber sample~1, make pH be about using the aqueous hydrochloric acid solution of 0.1M After 2.5, the sodium hydrate aqueous solution of 0.05M is added dropwise until pH reaches about 11, measures conductivity.Using following formula, by conductivity The amount of sodium hydroxide (V) that is consumed of neutralization stage of the slow weak acid of variation can determine amount of functional groups.Functional group's scale Show the amount of carboxyl.
Amount of functional groups [mmol/g]=V [ml] × 0.05/ cellulose nano-fibrous sample [g]
The cellulose nano-fibrous number average fiber diameter with carboxylate can be with fibre in structure used in the present invention The plain nanofiber of dimension is similary.
It is mixed about having the cellulose nano-fibrous of carboxylate in the structure in printed circuit board material in this case Dosage, relative to the entire amount of composition in addition to the solvents, the mass % of preferably 0.1 mass %~80, more preferably 0.2 matter Measure the mass % of %~70.The cellulose nano-fibrous blend amount in structure with carboxylate is more than 0.1 mass % Under, the desired effect of the present invention can be obtained well.On the other hand, in the case of below 80 mass %, Film making properties carry It is high.
In addition, the printed circuit board material of the present invention preferably comprises the number average fiber diameter manufactured by lignocellulosic and is Cellulose nano-fibrous (the hereinafter referred to lignocellulosic nanofiber) of 3nm~1000nm.The cellulose Nanowire as a result, Dimension can obtain as follows.It is high and can to obtain in the circuit of fine and high current purposes proof voltage between circuit The printed circuit board material of high insulating reliability is maintained for a long time.
(lignocellulosic nanofiber)
Lignocellulosic present in nature has cellulose and lignin and the three dimensional network of hemicellulose firm connection Network hierarchical structure, the cellulosic molecule in cell wall is not unimolecule, but regular collection and forms having for tens set Crystalline microfibre (cellulose nano-fibrous).Specifically, the lignocellulosic used in the present invention for example can be by wood Lignocellulosic biomass that the plants such as material or agricultural product, vegetation, cotton obtain or the bacteria cellulose generated by microorganism etc. obtain .It is cellulose nano-fibrous in order to be manufactured by lignocellulosic, the method for being coexisted with medium and carrying out mechanical crushing can be used.
As the mechanical crushing method, for example, ball mill (vibrator, rotating ball mill, planet-shaped ball Grinding machine) or rod mill, ball mill, disc mill, cutting crusher, hammer crusher, impeller grinding machine, extruder, mixer (height Fast rotation oar blade profile mixer, homomixer), homogenizer (high-pressure homogenizer, mechanical homogenizer, ultrasonic homogenizer) Deng.Among these, crushing preferably passes through ball mill, rod mill, ball mill, disc mill, cutting crusher, extruder or mixer Come carry out.By using these breaking methods, can relatively easily manufacture cellulose nano-fibrous.In addition, obtained fibre The deviation of the size of the plain nanofiber of dimension reduces.
As the medium used in pulverizing process, it is not particularly limited, it is preferable to use water, low molecular compound, macromolecule Compound or fatty acid etc..These can be used alone, and can also be use mixing two or more.It is excellent among these Choosing mixes water with low molecular compound, high-molecular compound or fatty acid, is used as crushing with medium.
As the low molecular compound in above-mentioned, alcohols, ethers, ketone, sulfoxide type, amides, amine, virtue can be enumerated The fragrant same clan, morpholine class, ionic liquid etc..In addition, as high-molecular compound, alcohol system high score subclass, ether system height can be enumerated Molecule class, amide system high score subclass, amine system high score subclass, aromatic system high score subclass etc..It, can be in addition, as fatty acid Enumerate saturated fat acids, unsaturated fatty acids etc..It should be noted that in this case, as used degraded Object, high-molecular compound and fatty acid are closed, it is preferable to use water-soluble substance.
In addition, before above-mentioned pulverizing process, in order to make crushing easy, the ozone treatment as pre-treatment can also be carried out Deng.
The number average fiber diameter of lignocellulosic nanofiber used in the present invention can be with above-mentioned cellulose Nanowire Dimension is similary.
About the blend amount of the above-mentioned lignocellulosic nanofiber in printed circuit board material in this case, relative to The mass % of the entire amount of composition in addition to aftermentioned organic solvent, preferably 0.1 mass %~80, more preferably 0.2 mass % ~70 mass %.In the case that cellulose nano-fibrous blend amount is more than 0.1 mass %, the present invention can be obtained well Desired effect.On the other hand, in the case of below 80 mass %, Film making properties improve.
Embodiment
In the following, the present invention is described in more detail using embodiment.It should be noted that the number in following tables represents Mass parts.
[synthesis example 1]
(varnish 1)
Into 2 liters of removable flasks for having blender, thermometer, reflux condenser, dropping funel and nitrogen ingress pipe Add in the diethylene glycol dimethyl ether 900g as solvent and the tert-butyl hydroperoxide 2 ethyl hexanoic acid ester (day as polymerization initiator Oily Co., Ltd.'s manufacture, trade name：PerbutylO) 21.4g is heated to 90 DEG C.After heating, it was added dropwise and is added in thereto with 3 hours Methacrylic acid 309.9g, methyl methacrylate 116.4g and lactone-modified 2-hydroxyethyl methacry-late (Co., Ltd. Daicel manufactures, trade name：PRAXCELL FM1) 109.8g and bis- (uncles 4- of dicetyl peroxydicarbonate as polymerization initiator Butylcyclohexyl) ester (Japan Oil Co's manufacture, trade name：PERROYL TCP)21.4g.In addition, cured 6 hours, by This obtains copolymer resins containing carboxyl.It should be noted that these reactions carry out in a nitrogen atmosphere.
Then, 3,4- epoxycyclohexyl methyl acrylates (Co., Ltd. is added in into obtained copolymer resins containing carboxyl Daicel manufactures, trade name：Cyclomer A200) 363.9g, the dimethyl benzyl amine 3.6g as ring opening catalyst, conduct The hydroquinone monomethyl ether 1.80g of polymerization inhibitor, is heated to 100 DEG C, and it is stirred, and the open loop addition for thus carrying out epoxy is anti- It should.After 16 hours, obtain the acid value comprising solid constituent be 108.9mgKOH/g, weight-average molecular weight 25,000 containing carboxylic The solution of 53.8 mass % (nonvolatile component) of base resin.
[synthesis example 2]
(varnish 2)
The diethyl two as solvent is added in into the flask for having thermometer, blender, dropping funel and reflux condenser Alcohol monoethyl ether acetate and the azodiisobutyronitrile as catalyst, were heated to 80 DEG C in a nitrogen atmosphere, with about 2 hours It is added dropwise methacrylic acid and methyl methacrylate with 0.40:The monomer that 0.60 molar ratio mixes.In addition, it is stirred After mixing 1 hour, 115 DEG C are raised the temperature to, its inactivation is made to obtain resin solution.
After the resin solution is cooled down, for the resin solution, using tetrabutylammonium bromide as catalyst, 95 DEG C~ Make butyl glycidyl ether under conditions of 105 DEG C, 30 hours with 0.40 molar ratio and the equivalent of the carboxyl of obtained resin Addition reaction is carried out, and is allowed to cool.
In addition, for the OH bases of resin obtained above, under conditions of 95 DEG C~105 DEG C, 8 hours, make tetrahydrochysene neighbour's benzene Dicarboxylic acid anhydride carries out addition reaction with 0.26 molar ratio.It is drawn off after cooling, obtaining the acid value comprising solid constituent is The solution of 78.1mgKOH/g, the 50 mass % (nonvolatile component) Han carboxy resin that weight-average molecular weight is 35,000.
[synthesis example 3]
(varnish 3)
Cresol novolak type ring is added in into the flask for having thermometer, blender, dropping funel and reflux condenser Oxygen resin (Dainippon Ink Chemicals's manufacture, EPICLON N-680, epoxide equivalent=210) 210g and the carbitol second as solvent Acid esters 96.4g makes its heating for dissolving.Then, it adds in thereto as the quinhydrones 0.1g of polymerization inhibitor and as catalysts Triphenylphosphine 2.0g.The mixture is heated to 95 DEG C~105 DEG C, acrylic acid 72g is added dropwise at leisure, it is made to react about 16 hours Until acid value reaches below 3.0mgKOH/g.After the reaction product is cooled to 80 DEG C~90 DEG C, tetrahydrophthalic acid is added in Acid anhydride 76.1g makes its reaction about 6 hours until understanding the absorption peak (1780cm of acid anhydrides by infrared absorptiometric analysis-1) until disappearance. The aromatic system solvent IPSOL#150 96.4g of Idemitsu Kosen Co., Ltd.'s manufacture are added in into the reaction solution, are taken after dilution Go out.The nonvolatile component of obtained carboxylic photosensitive polymer solution is 65 mass %, the acid value of solid constituent is 78mgKOH/g。
[making of cellulose nano-fibrous dispersion liquid]
To cellulose nano-fibrous (Co., Ltd. SUGINO MACHINE manufactures, 10 mass % celluloses of BiNFi-s, number Equal fibre diameter 80nm) dewatering and filtering is carried out, the carbitol acetate of 10 times of amounts of filtrate weight is added in, after stirring 30 minutes It is filtered.The replacement operator is repeated 3 times, the carbitol acetate of 10 times of amounts of filtrate weight is added in, makes 10 mass % Cellulose nano-fibrous dispersion liquid.
<Embodiment 1>
[table 1]
* 1-1) Thermocurable compound 1：828 Mitsubishi chemical Co., Ltd of Epikote manufactures
* 1-2) Thermocurable compound 2：807 Mitsubishi chemical Co., Ltd of Epikote manufactures
* 1-3) curing catalysts 1：2MZ-A Shikoku Chem manufactures
* 1-4) acrylic copolymer compound 1：BYK-361N BYK-CHEMIE Japan Co., Ltd. manufactures
* 1-5) acrylic copolymer compound 2：This chemical conversion of POLYFLOW No.50EHF (50 mass % of solid constituent) nanmus Co., Ltd. manufactures
* 1-6) acrylic copolymer compound 3：POLYFLOW No.90 this chemical conversion of nanmu Co., Ltd. manufactures
* 1-7) colorant：Phthalocyanine blue
* 1-8) organic solvent：Carbitol acetate
[table 2]
* 1-9) Thermocurable compound 3：UNIDIC V-8000 (40 mass % of solid constituent) Dainippon Ink Chemicals manufactures
* 1-10) Thermocurable compound 4：Denacol EX-830 Nagase chemteX Co., Ltd. manufactures
* 1-11) curing catalysts 2：Triphenylphosphine
* 1-12) photocurable compound 1：Bisphenol-a epoxy acrylate Mitsubishi chemical Co., Ltd manufactures
* 1-13) photocurable compound 2：Trimethylolpropane trimethacrylate
* 1-14) photocurable compound 3：KAYAMER PM2 Nippon Kayaku K. K manufactures
* 1-15) photocurable compound 4：LIGHT ESTER HO Kyoeisha Chemical Co., Ltd. manufactures
* 1-16) Photoepolymerizationinitiater initiater 1：2- ethyl hydrazine
[table 3]
* 1-17) thermoplastic resin 1：NOVATEC PP BC03L Japan Polypropylene Co., Ltd. manufactures
* 1-18) thermoplastic resin 2：Polyethylene Co., Ltd. of NOVATEC LD LC561 Japan manufactures
[table 4]
* 1-19) thermoplastic resin 3：ソ ク シ ー Le SOXR-OB, NIPPON KODOSHI CORPORATION manufacture Varnish (70 mass % of solid constituent, 30 mass % of N-Methyl pyrrolidone)
[preparation of composition]
About embodiment 1-1~embodiment 1-12 in above-mentioned Tables 1 and 2 and comparative example 1-1~comparative example 1-3 and Embodiment 1-19~embodiment 1-21 and comparative example 1-6 in above-mentioned table 4 carry out each ingredient mixture, stirring, make it with three rollers Dispersion, prepares composition respectively.
[making of composite shaped body]
About the embodiment 1-13~embodiment 1-15 and comparative example 1-4 in above-mentioned table 3, after each ingredient of mixture, using mixed Mill (torque rheometer (LABO PLASTOMILL), the manufacture of Toyo Seiki Co., Ltd.) is melted at 180 DEG C with rotating speed 70rpm It is kneaded 10 minutes.For obtained mixture, forcing press (LABOPRESS P2-30T, Toyo Seiki Co. Ltd. system are used Make) with 190 DEG C, the condition hot pressing of 0.5MPa 3 minutes, with 20MPa hot pressing 1 minute, and then cooled down with the condition of 23 DEG C, 0.5MPa Compacting 1 minute.The cellulose nano-fibrous composite shaped body for the sheet that thickness is 0.05mm is obtained as a result,.
About the embodiment 1-16~embodiment 1-18 and comparative example 1-5 in above-mentioned table 3, after each ingredient of mixture, using mixed Mill (torque rheometer (LABO PLASTOMILL), the manufacture of Toyo Seiki Co., Ltd.) is melted at 150 DEG C with rotating speed 70rpm It is kneaded 10 minutes.For obtained mixture, forcing press (LABOPRESS P2-30T, Toyo Seiki Co. Ltd. system are used Make) with 160 DEG C, the condition hot pressing of 0.5MPa 3 minutes, with 20MPa hot pressing 1 minute, and then cooled down with the condition of 23 DEG C, 0.5MPa Compacting 1 minute.The cellulose nano-fibrous composite shaped body for the sheet that thickness is 0.05mm is obtained as a result,.
(making of stain removability evaluation test film)
The definition graph for the production method for representing stain removability evaluation substrate is shown in FIG. 2.(a)~(c- in figure 1) it is vertical view, (c-2) is the sectional view of (c-1).As shown in Fig. 2, by silk screen print method by embodiment 1-1~embodiment 1- The composition of 6 and comparative example 1-1 print on insulating layer 13b be equipped with conductor layer 13a size be 50mm × 50mm, thickness is In the entire surface of the experiment substrate 13 of the FR-4 copper-coated laminates (18 μm thick with copper packing, copper) of 1.6mm, heated air circulation type is utilized Drying oven makes its curing with the condition of 140 DEG C, 30 minutes, forms insulating resin layer 14.Then, existed using carbon dioxide laser A diameter of 100 μm of hole (via hole) 15 is outputed on conductor layer 13a, has made test film.
The composition of embodiment 1-7~embodiment 1-9 and comparative example 1-2 is printed to above-mentioned experiment by silk screen print method The entire surface of substrate, using heated air circulation type drying oven with 100 DEG C, the drying of the condition of 30 minutes after, with 170 DEG C, 60 minutes Condition makes its curing, forms insulating resin layer, has made test film as described above in addition to this.
The composition of embodiment 1-10~embodiment 1-12 and comparative example 1-3 is printed to above-mentioned examination by silk screen print method The entire surface of substrate is tested, using metal halide lamp with the wavelength illumination 2J/cm of 350nm2Accumulated light, be solidified to form absolutely Edge resin layer, has made test film as described above in addition to this.
The cellulose that the thickness of embodiment 1-13~embodiment 1-18, comparative example 1-4 and comparative example 1-5 is 0.05mm is received Rice fiber composite formed body with 1 minute in 190 DEG C, the condition hot pressing to above-mentioned experiment substrate of 20MPa, and then with 23 DEG C, The condition cooling compacting of 0.5MPa 1 minute, forms insulating resin layer, has made test film as described above in addition to this.
The composition of embodiment 1-19~embodiment 1-21 and comparative example 1-6 is printed to above-mentioned examination by silk screen print method The entire surface of substrate is tested, after being dried using heated air circulation type drying oven with the condition of 120 DEG C, 10 minutes, with 250 DEG C, 30 minutes Condition cured, formed insulating resin layer, made test film as described above in addition to this.
(stain removability)
Using each test film in (the Rohm and Haas of CIRCUPOSIT MLB CONDITIONER 211 as swelling solution Society's manufacture, 200ml/l) and the mixed liquor of CIRCUPOSIT Z (Rohm and Haas societies manufacture, 100ml/l) in soaked in 80 DEG C Stain 5 minutes, then, in CIRCUPOSIT MLB PROMOTER 213A (the Rohm and Haas societies systems as roughening liquid Make, 100ml/l) and CIRCUPOSIT MLB PROMOTER 213B (Rohm and Haas societies manufacture, 150ml/l) mixing It is impregnated 10 minutes in 80 DEG C in liquid, finally, in the CIRCUPOSIT MLB NEUTRALIZER 216-2 (Rohm as neutralizer And Haas societies manufacture, 200ml/l) in 50 DEG C 5 minutes impregnate.Thereafter, scanning electron microscope (SEM, Japan's electricity are utilized Sub- Co., Ltd.'s manufacture JSM-6610LV, multiplying power：3,500 times) observation via hole bottom (copper surface), visual confirmation via hole bottom (copper surface) has free from smutting.Evaluation criteria is as follows.Evaluation result is shown in table 5 below and table 6.
(evaluation) zero：Free from smutting
×：There is stain
(making of heat resistance, acid resistance and evaluating pencil hardness test film)
On the experiment substrate of FR-4 copper-coated laminates (copper is 18 μm thick) that size is 50mm × 50mm, thickness is 1.6mm Insulating resin layer is formed, so as to make each test film.Above-mentioned insulating resin layer is in the note with stain removability evaluation test film It is formed under the conditions of carrying similarly.
(heat resistance)
Using above-mentioned each test film, after rosin series solder flux is coated with, 30 are flowed in 260 DEG C of solder bath is redefined for Second, after clean and dried with propylene glycol methyl ether acetate, cellophane adhesive tape is utilized to carry out disbonded test, it is thus identified that film stripping The presence or absence of.Evaluation criteria is as follows.Evaluation result is shown in table 5 below and table 6.
(evaluation) zero：Film is not removed completely.
×：Film produces stripping.
(acid resistance)
Using above-mentioned each test film, impregnated 60 minutes in 25 DEG C in the aqueous sulfuric acid of 10 capacity %, wash and make it It is dry.Later, disbonded test is carried out using cellophane adhesive tape, it is determined that the presence or absence of film stripping.Evaluation criteria with it is above-mentioned heat-resisting Property is identical.Evaluation result is shown in table 5 below and table 6.
(pencil hardness)
Using above-mentioned each test film, the pencil for B~9H that the tip of core is smoothed is pressed with about 45 ° of angle, The hardness of the pencil of film stripping does not occur for record.As a result it is shown in table 5 below and table 6.
(making of electrical insulating property evaluation test film)
Using the FR-4 copper-coated laminates (copper is 18 μm thick) that size is 100mm × 150mm, thickness is 1.6mm, pass through etching Engineering method makes the comb-type electrode pattern of IPC standard B patterns, as experiment substrate.On the experiment substrate, according to comb shape can be covered The mode of electrode portion forms insulating resin layer, so as to make each test film.Above-mentioned insulating resin layer is evaluated with stain removability With the record of test film it is same under the conditions of formed.
(electrical insulating property)
Using above-mentioned each test film, apply the bias of DC500V between comb poles, measure insulating resistance value.If value is More than 100G Ω are then denoted as zero, be denoted as if 100G Ω are less than ×.As a result it is shown in table 5 below and table 6.
(making of the peel strength evaluation test film of coating layer)
On the experiment substrate of FR-4 copper-coated laminates (copper is 18 μm thick) that size is 50mm × 50mm, thickness is 1.6mm Form insulating resin layer.Above-mentioned insulating resin layer shape under the conditions of the record with stain removability evaluation test film is same Into.Coating layer is formed followed by non-electrolytic copper-plating method, followed by entire surface of the copper electroplating method on insulating resin layer, from And make each test film.
(peeling strength test (peeling strength test) of coating layer)
Cut on the coating layer of each test film width 10mm, long 100mm part notch, one end is peeled and uses folder Tool is clamped, and measures the load when vertical direction peels 35mm with the speed of 50mm/ minutes at room temperature.If 0.8kN/m with On be then denoted as zero, if less than be denoted as if 0.8kN/m ×.As a result it is shown in table 5 below and table 6.
[table 5]
[table 6]
As described above in detail, it is known that：If using the printed circuit board material of the present invention, it is difficult to generate copper etc. The stain of metal foil upper surface, even and if generation also easily removing.In addition, it confirms：The printed circuit board material of the present invention There is sufficient characteristic as solder resist and interlayer dielectic.
<Embodiment 2>
[making of evaluation piece]
Record in table 7 below makes its dispersion with three rollers, makes each composition come mixture, each ingredient of stirring.Relatively In the entire amount of composition in addition to the solvents, cellulose nano-fibrous and phyllosilicate additive amount is respectively 10 mass %. Then, the composition is printed to the entire surface for the copper foil that thickness is 18 μm by silk screen print method, is done using heated air circulation type Dry stove makes its curing with the condition of 140 DEG C, 30 minutes.Later, copper foil is removed, makes the piece that thickness is 50 μm.
[evaluation of linear expansion coefficient]
The piece of above-mentioned making is cut into wide 3mm × long 30mm.For the piece, SII TMA are used (Thermomechanical Analysis, thermo-mechanical analysis) " EXSTAR6000 ", the 10mm between stretch mode, collet, load 30mN is in a nitrogen atmosphere with 5 DEG C/min from room temperature to 200 DEG C, next, being cooled to 20 with 5 DEG C/min from 200 DEG C ℃.Later, by linear expansion coefficient is obtained from the measured value of 30 DEG C when being warming up to 200 DEG C for 20 DEG C~100 DEG C with 5 DEG C/min.It comments Valency result is shown in Table 7.
[table 7]
* 2-1) Thermocurable compound 1：828 Mitsubishi chemical Co., Ltd of Epikote manufactures
* 2-2) Thermocurable compound 2：807 Mitsubishi chemical Co., Ltd of Epikote manufactures
* 2-3) curing catalysts 1：2MZ-A Shikoku Chem manufactures
* 2-4) colorant：Phthalocyanine blue
* 2-5) phyllosilicate：LUCENTITE STN Co-op Chemical Co., Ltd. manufactures
* 2-6) organic solvent：Carbitol acetate
Record in table 8 below makes its dispersion with three rollers, makes each composition come mixture, each ingredient of stirring.Relatively In the entire amount of composition in addition to the solvents, cellulose nano-fibrous and phyllosilicate additive amount is respectively 10 mass %. Then, the composition is printed to the entire surface for the copper foil that thickness is 18 μm by silk screen print method, is done using heated air circulation type After dry stove is dried with the condition of 100 DEG C, 30 minutes, its curing is made with the condition of 170 DEG C, 60 minutes.Later, copper foil is removed, is surveyed The linear expansion coefficient for the piece that fixed obtained thickness is 50 μm.
[table 8]
* 2-7) Thermocurable compound 3：UNIDIC V-8000 (40 mass % of solid constituent) Dainippon Ink Chemicals manufactures
* 2-8) Thermocurable compound 4：Denacol EX-830 Nagase chemteX Co., Ltd. manufactures
* 2-9) curing catalysts 2：Triphenylphosphine
Record in table 9 below uses kneading machine (torque rheometer (LABO come each ingredient of mixture PLASTOMILL), Toyo Seiki Co., Ltd. manufactures) at 180 DEG C with rotating speed 70rpm melting mixings 10 minutes.Relative to except molten The entire amount of composition outside agent, cellulose nano-fibrous and phyllosilicate additive amount is respectively 10 mass %.For institute Obtained mixture, using forcing press (LABOPRESS P2-30T, Toyo Seiki Co., Ltd. manufacture) with 190 DEG C, 0.5MPa Condition hot pressing 3 minutes, with 20MPa hot pressing 1 minute, and then with the condition cooling compacting 1 minute of 23 DEG C, 0.5MPa.It surveys as a result, The linear expansion coefficient for the piece that fixed obtained thickness is 50 μm.
[table 9]
* 2-10) thermoplastic resin 1：NOVATEC PP BC03L Japan Polypropylene Co., Ltd. manufactures
Record in table 10 below uses kneading machine (torque rheometer (LABO come each ingredient of mixture PLASTOMILL), Toyo Seiki Co., Ltd. manufactures) at 150 DEG C with rotating speed 70rpm melting mixings 10 minutes.Relative to except molten The entire amount of composition outside agent, cellulose nano-fibrous and phyllosilicate additive amount is respectively 10 mass %.For institute Obtained mixture, using forcing press (LABOPRESS P2-30T, Toyo Seiki Co., Ltd. manufacture) with 160 DEG C, 0.5MPa Condition hot pressing 3 minutes, with 20MPa hot pressing 1 minute, and then with the condition cooling compacting 1 minute of 23 DEG C, 0.5MPa.It surveys as a result, The linear expansion coefficient for the piece that fixed obtained thickness is 50 μm.
[table 10]
* 2-11) thermoplastic resin 2：Polyethylene Co., Ltd. of NOVATEC LD LC561 Japan manufactures
Record in table 1 below 1 makes its dispersion with three rollers, makes each composition come mixture, each ingredient of stirring.Phase For the entire amount of composition in addition to the solvents, cellulose nano-fibrous and phyllosilicate additive amount is respectively 10 matter Measure %.Then, the composition is printed to the entire surface for the copper foil that thickness is 18 μm by silk screen print method, utilizes hot air circulation After formula drying oven is dried with the condition of 120 DEG C, 10 minutes, its curing is made with the condition of 250 DEG C, 30 minutes.Later, copper is removed Foil measures the linear expansion coefficient for the piece that obtained thickness is 50 μm.
[table 11]
* 2-12) thermoplastic resin 3：ソ ク シ ー Le SOXR-OB NIPPON KODOSHI CORPORATION manufactures Varnish (70 mass % of solid constituent)
Record in table 1 below 2 makes its dispersion with three rollers, makes each composition come mixture, each ingredient of stirring.Phase For the entire amount of composition in addition to the solvents, cellulose nano-fibrous and phyllosilicate additive amount is respectively 10 matter Measure %.Then, the composition is printed to the entire surface for the copper foil that thickness is 18 μm by silk screen print method, utilizes metal halide Object lamp is with the wavelength illumination 2J/cm of 350nm2Accumulated light, make its curing.Later, copper foil is removed, measures obtained thickness Linear expansion coefficient for 50 μm of piece.
[table 12]
* 2-13) photocurable compound 1：Bisphenol-a epoxy acrylate Mitsubishi chemical Co., Ltd manufactures
* 2-14) photocurable compound 2：Trimethylolpropane trimethacrylate
* 2-15) photocurable compound 3：KAYAMER PM2 Nippon Kayaku K. K manufactures
* 2-16) photocurable compound 4：LIGHT ESTER HO Kyoeisha Chemical Co., Ltd. manufactures
* 2-17) Photoepolymerizationinitiater initiater 1：2- ethyl hydrazine
Record in 3~table of table 1 below 15 makes its dispersion with three rollers, makes each combination come mixture, each ingredient of stirring Object.Relative to the entire amount of composition in addition to the solvents, cellulose nano-fibrous and phyllosilicate additive amount is respectively 10 Quality %.Then, the composition is printed to the entire surface for the copper foil that thickness is 18 μm by silk screen print method, is followed using hot wind Ring drying stove is made it dry with the condition of 80 DEG C, 30 minutes.Then, using the minus figure that can cover experiment substrate edges portion Case, using use in printed circuit board exposure machine HMW-680GW (ORC Mfg. Co., Ltd.'s manufacture) with 700mJ/cm2Accumulation light Amount is exposed, and using 30 DEG C, 1% aqueous sodium carbonate as developer solution, is developed 60 seconds using use in printed circuit board developing machine, Edge part is removed.Then, using heated air circulation type drying oven in 150 DEG C of heat cures 60 minutes.Later, copper foil is removed, is measured Obtained thickness is the linear expansion coefficient of 50 μm of piece.
[table 13]
* 2-18) curing catalysts 3：Crushing of Ultrafine melamine Misao Kusano manufactures
* 2-19) curing catalysts 4：Dicyandiamide
* 2-20) Photoepolymerizationinitiater initiater 2：907 BASF societies of Irgacure manufacture
* 2-21) photocurable compound 5：Dipentaerythritol tetraacrylate
* 2-22) Thermocurable compound 5：TEPIC-H Misao Kusano manufactures
[table 14]
[table 15]
As described above in detail, it confirms：It is if cellulose nano-fibrous and phyllosilicate using having shared Insulating materials, then linear expansion coefficient reduce tremendously.
<Embodiment 3>
[table 16]
* 3-1) Thermocurable compound 1：828 Mitsubishi chemical Co., Ltd of Epikote manufactures
* 3-2) Thermocurable compound 2：807 Mitsubishi chemical Co., Ltd of Epikote manufactures
* 3-3) curing catalysts 1：2MZ-A Shikoku Chem manufactures
* 3-4) colorant：Phthalocyanine blue
* 3-5) organo-silicon compound 1：BYK-313 (15 mass % of solid constituent) BYK-CHEMIE Japan Co., Ltd. Manufacture
* 3-6) organo-silicon compound 2：SH-8400TORAY DOW CORNING Co., Ltd. manufactures
* 3-7) organo-silicon compound 3：The Chemical Co., Ltd. manufacture of KS-66 SHIN-ETSU HANTOTAIs
* 3-8) fluorine compounds 1：MEGAFAC RS-75 (40 mass % of solid constituent) Dainippon Ink Chemicals manufactures
* 3-9) fluorine compounds 2：AashiGuard AG-E300D (30 mass % of solid constituent) Asahi Glass Co., Ltd's system It makes
* 3-10) organic solvent：Carbitol acetate
[table 17]
* 3-11) Thermocurable compound 3：UNIDIC V-8000 (40 mass % of solid constituent) Dainippon Ink Chemicals manufactures
* 3-12) Thermocurable compound 4：Denacol EX-830 Nagase chemteX Co., Ltd. manufactures
* 3-13) Thermocurable compound 5：TEPIC-H Misao Kusano manufactures
* 3-14) thermoplastic resin 1：NOVATEC PPBC03L Japan Polypropylene Co., Ltd. manufactures
* 3-15) thermoplastic resin 2：Polyethylene Co., Ltd. of NOVATEC LDLC561 Japan manufactures
* 3-16) thermoplastic resin 3：ソ ク シ ー Le SOXR-OB (70 mass % of solid constituent) NIPPON KODOSHI The varnish of CORPORATION manufactures
* 3-17) photocurable compound 1：Bisphenol-a epoxy acrylate Mitsubishi chemical Co., Ltd manufactures
* 3-18) photocurable compound 2：Trimethylolpropane trimethacrylate
* 3-19) photocurable compound 3：KAYAMER PM2 Nippon Kayaku K. K manufactures
* 3-20) photocurable compound 4：LIGHT ESTER HO Kyoeisha Chemical Co., Ltd. manufactures
* 3-21) photocurable compound 5：Dipentaerythritol tetraacrylate
* 3-22) curing catalysts 2：Triphenylphosphine
* 3-23) curing catalysts 3：Crushing of Ultrafine melamine Misao Kusano manufactures
* 3-24) curing catalysts 4：Dicyandiamide
* 3-25) Photoepolymerizationinitiater initiater 1：2- ethyl hydrazine
* 3-26) Photoepolymerizationinitiater initiater 2：907 BASF societies of Irgacure manufacture
[table 18]
In above-mentioned table proportioning (not including embodiment 3-14, embodiment 3-15, embodiment 3-22, embodiment 3-23, Comparative example 3-3 and comparative example 3-4) come mixture, each ingredient of stirring, make its dispersion with three rollers, make composition respectively.It needs It is bright, the digital representation mass parts in table.
About embodiment 3-14, embodiment 3-22 and comparative example 3-3, each ingredient of mixture uses kneading machine (torque rheometer (LABO PLASTOMILL), Toyo Seiki Co., Ltd. manufacture) at 180 DEG C with rotating speed 70rpm melting mixings 10 minutes.For Obtained mixture, using forcing press (LABOPRESS P2-30T, Toyo Seiki Co., Ltd. manufacture) with 190 DEG C, The condition hot pressing of 0.5MPa 3 minutes with 20MPa hot pressing 1 minute, and then is suppressed 1 minute with the condition cooling of 23 DEG C, 0.5MPa. The cellulose nano-fibrous composite shaped body for the sheet that thickness is 0.5mm and 0.05mm is obtained as a result,.
About embodiment 3-15, embodiment 3-23 and comparative example 3-4, each ingredient of mixture uses kneading machine (torque rheometer (LABO PLASTOMILL), Toyo Seiki Co., Ltd. manufacture) at 150 DEG C with rotating speed 70rpm melting mixings 10 minutes.For Obtained mixture, using forcing press (LABOPRESS P2-30T, Toyo Seiki Co., Ltd. manufacture) with 160 DEG C, The condition hot pressing of 0.5MPa 3 minutes with 20MPa hot pressing 1 minute, and then is suppressed 1 minute with the condition cooling of 23 DEG C, 0.5MPa. The cellulose nano-fibrous composite shaped body for the sheet that thickness is 0.5mm and 0.05mm is obtained as a result,.
[evaluation as interlayer dielectic]
(making of test film)
The definition graph of the production method for the evaluation substrate for representing interlayer dielectic is shown in FIG. 3.(a) in figure~ (e-1) it is vertical view, (e-2) is the sectional view of (e-1).As shown in figure 3, by silk screen print method by embodiment 3-1~implementation Example 3-12 and comparative example 3-1 composition print on insulating layer 21b be equipped with conductor layer 21a size for 50mm × 50mm, In the entire surface of the experiment substrate 21 of FR-4 copper-coated laminates (18 μm thick with copper packing, copper) that thickness is 1.6mm, hot wind is utilized Circulating drying oven makes its curing with the condition of 140 DEG C, 30 minutes, forms insulating resin layer 22.Then, swashed using carbon dioxide Light device outputs a diameter of 100 μm of hole (via hole) 23 on conductor layer 21a, removes decontamination using potassium permanganate solution later Mark carries out entire surface non-electrolytic copper facing, then carries out electrolytic copper plating, forms coating layer 24.In addition, it is formed using engineering method is etched Wiring pattern 26, so as to make test film.Symbol 25 in figure represents corrosion-resisting pattern.
The composition of embodiment 3-13, embodiment 3-21 and comparative example 3-2 are printed to above-mentioned examination by silk screen print method The entire surface of substrate is tested, after being dried using heated air circulation type drying oven with the condition of 100 DEG C, 30 minutes, with 170 DEG C, 60 minutes Condition make its curing.Then, Wiring pattern is formed as described above, so as to make test film.
For by embodiment 3-14, embodiment 3-15, embodiment 3-22, embodiment 3-23, comparative example 3-3 and comparative example 3- The above-mentioned cellulose nano-fibrous composite shaped body for the sheet that 4 thickness formed are 0.05mm, with 190 on above-mentioned experiment substrate DEG C, 20MPa hot pressing 1 minute, and then with 23 DEG C, 0.5MPa coolings compacting 1 minute.Then, wiring diagram is formed as described above Case, so as to make test film.
The composition of embodiment 3-16, embodiment 3-24 and comparative example 3-5 are printed to above-mentioned examination by silk screen print method The entire surface of substrate is tested, after being dried using heated air circulation type drying oven with the condition of 120 DEG C, 10 minutes, with 250 DEG C, 30 minutes Condition make its curing.Then, Wiring pattern is formed as described above, so as to make test film.
The composition of embodiment 3-17, embodiment 3-25 and comparative example 3-6 are printed to above-mentioned examination by silk screen print method The entire surface of substrate is tested, using metal halide lamp with the wavelength illumination 2J/cm of 350nm2Accumulated light, make its curing.It connects It, forms Wiring pattern as described above, so as to make test film.
By silk screen print method by embodiment 3-18~embodiment 3-20, embodiment 3-26~embodiment 3-28 and comparative example The composition of 3-7~comparative example 3-9 is printed to entire surface, 30 minutes dry at 80 DEG C using heated air circulation type drying oven.Then, Using the negative pattern that can cover experiment substrate edges portion, use in printed circuit board exposure machine HMW-680GW (Co., Ltd. is utilized Manufactured by ORC makes) with 700mJ/cm2Accumulated light be exposed, using 30 DEG C, 1% aqueous sodium carbonate as development Liquid is developed 60 seconds using use in printed circuit board developing machine, then hot with heated air circulation type drying oven at 150 DEG C for edge part Curing 60 minutes.Then, Wiring pattern is formed as described above, so as to make test film.
(insulating reliability evaluation)
The DC voltage of 50V is applied to the electrode of 6 test films, placement experiment is carried out under 130 DEG C, 85% atmosphere. Insulation resistance is measured in test flume, record become by the insulating resistance value behind after on-test 1 hour 1/100th time. Even if in the case of having spent 100 hours insulating resistance value also do not decline, using at this as terminating.It the results are shown in following tables In.
[table 19]
[table 20]
[table 21]
[evaluation as core material]
(making of cellulose nano-fibrous)
About cellulose nano-fibrous, 0.2 mass % water slurries are made using distilled water, are carried out using glass filter It filters and forms a film, the piece that making size is 50mm × 50mm, thickness is 40 μm.
(embodiment 3-29)
828 50 mass parts of Epikote of Mitsubishi chemical Co., Ltd's manufacture, Mitsubishi chemical Co., Ltd are manufactured 807 50 mass parts of Epikote, acrylic copolymer compound (BYK-361N BYK-CHEMIE Japan Co. Ltd. systems Make) 1 mass parts, Shikoku Chem manufacture 3 mass parts of 2MZ-A, BYK-CHEMIE Japan Co. Ltd. systems 2 mass parts of BYK-313 and 100 mass parts of methyl ethyl ketone made carry out mixture, stirring, make resin solution.It is allowed to penetrate into It each cellulose nano-fibrous, is taken out after being placed 12 hours under 50 DEG C of atmosphere, it is 5 hours dry at 80 DEG C, make prepreg. 10 prepregs are overlapped, and then overlapped thickness is 18 μm of copper foil in table, using vacuum press with 160 DEG C of temperature, The condition of pressure 2MPa cures 3 hours.Then, as shown in (a)~(c) of Fig. 4, the exhausted of conductor layer 21a is formed on the two sides On the laminate 21 that edge layer 21b is formed, hole diameter is outputed as 300 μm of through hole 27 using spacing 5mm by Drilling operation.It Afterwards, stain is removed using potassium permanganate solution, progress electroless plating Copper treatment, then progress electrolytic copper plating covers processing, is formed Through-hole 28.Then, as shown in (a)~(c) of Fig. 5, Wiring pattern 26 is made using engineering method is etched, obtains test film.
(embodiment 3-30)
828 50 mass parts of Epikote of Mitsubishi chemical Co., Ltd's manufacture, Mitsubishi chemical Co., Ltd are manufactured 807 50 mass parts of Epikote, acrylic copolymer compound (BYK-361N BYK-CHEMIE Japan Co. Ltd. systems Make) 1 mass parts, Shikoku Chem manufacture 3 mass parts of 2MZ-A, Dainippon Ink Chemicals manufacture MEGAFAC 0.75 mass parts of RS-75 and 100 mass parts of methyl ethyl ketone carry out mixture, stirring, make resin solution, in addition to this with reality It applies a 3-29 and similarly obtains test film.
(comparative example 3-10)
828 50 mass parts of Epikote of Mitsubishi chemical Co., Ltd's manufacture, Mitsubishi chemical Co., Ltd are manufactured 807 50 mass parts of Epikote, 3 mass parts of 2MZ-A and methyl ethyl ketone 100 of Shikoku Chem's manufacture Mass parts carry out mixture, stirring, make resin solution, obtain test film in the same manner as embodiment 3-29 in addition to this.
(embodiment 3-31)
By 100 mass parts of UNIDIC V-8000 of Dainippon Ink Chemicals's manufacture, the manufacture of Nagase chemteX Co., Ltd. 23 mass parts of Denacol EX-830, (the Japan plants of formula meetings of BYK-361N BYK-CHEMIE of acrylic copolymer compound Society manufacture) 1 mass parts, 1 mass parts of triphenylphosphine, BYK-CHEMIE Japan Co., Ltd. manufacture 2 mass parts of BYK-313, Mixture, stirring are carried out with 100 mass parts of methyl ethyl ketone, makes resin solution, in addition to this in the same manner as embodiment 3-29 To test film.
(embodiment 3-32)
By 100 mass parts of UNIDIC V-8000 of Dainippon Ink Chemicals's manufacture, the manufacture of Nagase chemteX Co., Ltd. 23 mass parts of Denacol EX-830, (the Japan plants of formula meetings of BYK-361N BYK-CHEMIE of acrylic copolymer compound Society manufacture) 1 mass parts, 1 mass parts of triphenylphosphine, Dainippon Ink Chemicals manufacture 0.75 mass parts of MEGAFAC RS-75, He Jia 100 mass parts of base ethyl ketone carry out mixture, stirring, make resin solution, are tried in the same manner as embodiment 3-29 in addition to this Test piece.
(comparative example 3-11)
By 100 mass parts of UNIDIC V-8000 of Dainippon Ink Chemicals's manufacture, the manufacture of Nagase chemteX Co., Ltd. 23 mass parts of Denacol EX-830,1 mass parts of triphenylphosphine and 100 mass parts of methyl ethyl ketone carry out mixture, stirring, Resin solution is made, obtains test film in the same manner as embodiment 3-29 in addition to this.
(embodiment 3-33)
By 100 mass parts of ソ ク シ ー Le SOXR-OB of NIPPON KODOSHI CORPORATION manufactures, acrylic acid It is copolymerization (manufacture of BYK-361N BYK-CHEMIE Japan Co., Ltd.) 1 mass parts, Japan plants of BYK-CHEMIE 1.3 mass parts of BYK-313 and 70 mass parts of methyl ethyl ketone of formula commercial firm manufacture carry out mixture, stirring, make resin solution, In addition to this test film is obtained in the same manner as embodiment 3-29.
(embodiment 3-34)
By 100 mass parts of ソ ク シ ー Le SOXR-OB of NIPPON KODOSHI CORPORATION manufactures, acrylic acid It is copolymerization (manufacture of BYK-361N BYK-CHEMIE Japan Co., Ltd.) 1 mass parts, MEGAFAC RS-75 0.5 Mass parts and 70 mass parts of methyl ethyl ketone carry out mixture, stirring, make resin solution, same with embodiment 3-29 in addition to this Obtain test film to sample.
(comparative example 3-12)
By 100 mass parts of ソ ク シ ー Le SOXR-OB and methyl of NIPPON KODOSHI CORPORATION manufactures 70 mass parts of ethyl ketone carry out mixture, stirring, make resin solution, are tested in the same manner as embodiment 3-29 in addition to this Piece.
(embodiment 3-35)
The table inner layer of the above-mentioned cellulose nano-fibrous composite shaped body of sheet for being 0.5mm in the thickness of embodiment 3-14 Copper foil 18 μm folded is heated 1 minute using vacuum press with 190 DEG C of temperature, the condition of pressure 0.5MPa.Then, such as Fig. 4 (a) shown in~(c), be formed on the two sides on the laminate 21 that the insulating layer 21b of conductor layer 21a is formed, by drilling plus Work outputs hole diameter as 300 μm of through hole 27 using spacing 5mm.Later, stain is removed using potassium permanganate solution, carried out non- Electrolytic copper plating processing, then progress electrolytic copper plating covers processing, forms through-hole 28.Then, it as shown in (a)~(c) of Fig. 5, utilizes It etches engineering method and makes Wiring pattern 26, obtain test film.
(embodiment 3-36)
Other than the thickness for using embodiment 3-22 is the piece of 0.5mm, makes and be tested in the same manner as embodiment 3-35 Piece.
(comparative example 3-13)
Other than the thickness for using comparative example 3-3 is the piece of 0.5mm, makes and be tested in the same manner as embodiment 3-35 Piece.
(embodiment 3-37)
Other than the thickness for using embodiment 3-15 is the piece of 0.5mm, makes and be tested in the same manner as embodiment 3-35 Piece.
(embodiment 3-38)
Other than the piece of thickness 0.5mm for using embodiment 3-23, test film has been made in the same manner as embodiment 3-35.
(comparative example 3-14)
Other than the piece of thickness 0.5mm for using comparative example 3-4, test film has been made in the same manner as embodiment 3-35.
(insulating reliability evaluation)
The DC voltage of 50V is applied to the electrode of 6 test films, placement experiment is carried out under 130 DEG C, 85% atmosphere. Insulation resistance is measured in test flume, record by the insulating resistance value behind after on-test 1 hour become its 1/100th when Between.Even if in the case of having spent 100 hours insulating resistance value also do not decline, using at this as terminating.
[table 22]
[table 23]
As described above in detail, it confirms：By any one in organo-silicon compound and fluorine compounds or The presence of the two, the insulating reliability for being added to cellulose nano-fibrous insulating materials by tremendous improve.
<Embodiment 4>
[making of cellulose fibre dispersion liquid]
Mechanical treatment is carried out to coniferous tree sulfate pulp (NBKP) using high pressure homogenizer, by the equal fiber of obtained number A diameter of 3 μm of cellulose fibre is added in water and is sufficiently stirred, and makes the water slurry that cellulose fibre is 10 mass %. Dewatering and filtering is carried out to it, adds in the carbitol acetate of 10 times of amounts of filtrate weight, stirring is filtered after 30 minutes.Weight Multiple 3 replacement operators add in the carbitol acetate of 10 times of amounts of filtrate weight, make the cellulose fibre of 10 mass % Dispersion liquid.
[evaluation]
Record in table 2 below 4 and table 25 makes its dispersion with three rollers, makes each combination come mixture, each ingredient of stirring Object.Obtained composition is printed to the FR-4 that size is 150mm × 100mm, thickness is 1.6mm by silk screen print method and is applied The entire surface of copper laminated board (copper is 18 μm thick), makes its curing using heated air circulation type drying oven with the condition of 140 DEG C, 30 minutes. Film thickness after curing is 50 μm.Later, the surface roughening of solidfied material is made using potassium permanganate solution, entire surface is carried out non- Electrolytic copper plating then carries out electrolytic copper plating, makes evaluation substrate.Cut in copper facing portion width 10mm, the part of long 100mm is cut Mouthful, one end is peeled and is clamped with fixture, is measured at room temperature with the speed of 50mm/ minutes when vertical direction peels 35mm Load (peel strength).
[table 24]
* 4-1) Thermocurable compound 1：828 Mitsubishi chemical Co., Ltd of Epikote manufactures
* 4-2) Thermocurable compound 2：807 Mitsubishi chemical Co., Ltd of Epikote manufactures
* 4-3) curing catalysts 1：2MZ-A Shikoku Chem manufactures
* 4-4) colorant：Phthalocyanine blue
* 4-5) organic solvent：Carbitol acetate
[table 25]
Record in table 2 below 6 and table 27 makes its dispersion with three rollers, makes each combination come mixture, each ingredient of stirring Object.Obtained composition is printed to the FR-4 that size is 150mm × 100mm, thickness is 1.6mm by silk screen print method and is applied The entire surface of copper laminated board (copper is 18 μm thick), after being dried using heated air circulation type drying oven with the condition of 100 DEG C, 30 minutes, with 170 DEG C, the condition of 60 minutes make its curing.Film thickness after curing is 50 μm.Later, make solidfied material using potassium permanganate solution Surface roughening, non-electrolytic copper facing is carried out to entire surface, then carries out electrolytic copper plating, makes evaluation substrate.It is cut in copper facing portion Open wide 10mm, long 100mm part notch, one end is peeled and is clamped with fixture, is measured at room temperature with 50mm/ minutes Load (peel strength) of the speed when vertical direction peels 35mm.
[table 26]
* 4-6) Thermocurable compound 3：UNIDIC V-8000 (40 mass % of solid constituent) Dainippon Ink Chemicals manufactures
* 4-7) Thermocurable compound 4：Denacol EX-830Nagase chemteX Co., Ltd. manufactures
* 4-8) curing catalysts 2：Triphenylphosphine
[table 27]
Record in table 2 below 8 and table 29 uses kneading machine (torque rheometer (LABO come each ingredient of mixture PLASTOMILL), Toyo Seiki Co., Ltd. manufactures) at 180 DEG C with rotating speed 70rpm melting mixings 10 minutes.For acquired Mixture, using forcing press (LABOPRESS P2-30T, Toyo Seiki Co., Ltd. manufacture) with 190 DEG C, the item of 0.5MPa Part hot pressing 3 minutes with 20MPa hot pressing 1 minute, and then is suppressed 1 minute with the condition cooling of 23 DEG C, 0.5MPa.Thickness is obtained as a result, Spend the piece for 50 μm.It is as 150mm × 100mm, thickness by the piece hot pressing to size using the condition of 190 DEG C, 20MPa by hot pressing FR-4 copper-coated laminates (copper is 18 μm thick) upper 1 minute of 1.6mm, and then suppressed 1 minute with 23 DEG C, 0.5MPa coolings, it makes Test film.Later, the surface roughening of solidfied material is made using potassium permanganate solution, non-electrolytic copper facing is carried out to entire surface, is connect Carry out electrolytic copper plating, makes evaluation substrate.Cut in copper facing portion width 10mm, long 100mm part notch, one end is shelled It is clamped down and with fixture, measures (removed strong with load of the speed of 50mm/ minutes when vertical direction peels 35mm at room temperature Degree).
[table 28]
* 4-9) thermoplastic resin 1：NOVATEC PP BC03L Japan Polypropylene Co., Ltd. manufactures
[table 29]
Record in Table 3 below 0 and table 31 uses kneading machine (torque rheometer come each ingredient of mixture (LABOPLASTOMILL), Toyo Seiki Co., Ltd. manufactures) at 150 DEG C with rotating speed 70rpm melting mixings 10 minutes.For institute Obtained mixture, using forcing press (LABOPRESS P2-30T, Toyo Seiki Co., Ltd. manufacture) with 160 DEG C, 0.5MPa Condition hot pressing 3 minutes, with 20MPa hot pressing 1 minute, and then with the condition cooling compacting 1 minute of 23 DEG C, 0.5MPa.As a result, To the piece that thickness is 50 μm.By hot pressing using 190 DEG C, the condition of 20MPa by the piece hot pressing to size as 150mm × 100mm, thickness FR-4 copper-coated laminates (copper is 18 μm thick) upper 1 minute for 1.6mm is spent, and then is suppressed 1 minute with 23 DEG C, 0.5MPa coolings, system It is tested piece.Later, the surface roughening of solidfied material is made using potassium permanganate solution, electroless plating is carried out to entire surface Copper then carries out electrolytic copper plating, makes evaluation substrate.Cut in copper facing portion width 10mm, long 100mm part notch, by it One end peels and is clamped with fixture, measures the load when vertical direction peels 35mm with the speed of 50mm/ minutes at room temperature (peel strength).
[table 30]
* 4-10) thermoplastic resin 2：Polyethylene Co., Ltd. of NOVATEC LDLC561 Japan manufactures
[table 31]
Record in Table 3 below 2 and table 33 makes its dispersion with three rollers, makes each combination come mixture, each ingredient of stirring Object.Obtained composition is printed to the FR-4 that size is 150mm × 100mm, thickness is 1.6mm by silk screen print method and is applied The entire surface of copper laminated board (copper is 18 μm thick), after being dried using heated air circulation type drying oven with the condition of 120 DEG C, 10 minutes, with 250 DEG C, the condition of 30 minutes make its curing.Film thickness after curing is 50 μm.Later, make solidfied material using potassium permanganate solution Surface roughening, non-electrolytic copper facing is carried out to entire surface, then carries out electrolytic copper plating, makes evaluation substrate.It is cut in copper facing portion Open wide 10mm, long 100mm part notch, one end is peeled and is clamped with fixture, is measured at room temperature with 50mm/ minutes Load (peel strength) of the speed when vertical direction peels 35mm.
[table 32]
* 4-11) thermoplastic resin 3：ソ ク シ ー Le SOXR-OB NIPPON KODOSHI CORPORATION manufactures Varnish (70 mass % of solid constituent)
[table 33]
Record in Table 3 below 4 and table 35 makes its dispersion with three rollers, makes each combination come mixture, each ingredient of stirring Object.Obtained composition is printed to the FR-4 that size is 150mm × 100mm, thickness is 1.6mm by silk screen print method and is applied The entire surface of copper laminated board (copper is 18 μm thick), using metal halide lamp with the wavelength illumination 2J/cm of 350nm2Accumulated light, Make its curing.Film thickness after curing is 50 μm.Later, the surface roughening of solidfied material is made using potassium permanganate solution, to whole A face carries out non-electrolytic copper facing, then carries out electrolytic copper plating, makes evaluation substrate.Cut in copper facing portion width 10mm, long 100mm One end is peeled and is clamped with fixture by partial notch, measures shelled with the speed of 50mm/ minutes in vertical direction at room temperature Load (peel strength) during lower 35mm.
[table 34]
* 4-12) photocurable compound 1：Bisphenol-a epoxy acrylate Mitsubishi chemical Co., Ltd manufactures
* 4-13) photocurable compound 2：Trimethylolpropane trimethacrylate
* 4-14) photocurable compound 3：KAYAMER PM2 Nippon Kayaku K. K manufactures
* 4-15) photocurable compound 4：LIGHT ESTER HO Kyoeisha Chemical Co., Ltd. manufactures
* 4-16) Photoepolymerizationinitiater initiater 1：2- ethyl hydrazine
[table 35]
Record in 6~table of Table 3 below 41 makes its dispersion with three rollers, makes each combination come mixture, each ingredient of stirring Object.Obtained composition is printed to the FR-4 that size is 150mm × 100mm, thickness is 1.6mm by silk screen print method and is applied The entire surface of copper laminated board (copper is 18 μm thick), it is 30 minutes dry at 80 DEG C using heated air circulation type drying oven.Then, using can cover The negative pattern in lid experiment substrate edges portion, utilizes use in printed circuit board exposure machine HMW-680GW (ORC Mfg. Co., Ltd. Manufacture) with 700mJ/cm2Accumulated light be exposed, using 30 DEG C, 1% aqueous sodium carbonate as developer solution, utilize print Printed circuit board is developed 60 seconds with developing machine, for edge part, is then divided at 150 DEG C with heated air circulation type drying oven heat cure 60 Clock.Film thickness after curing is 50 μm.Later, the surface roughening of solidfied material is made using potassium permanganate solution, to entire surface into The copper facing of row non-electrolytic then carries out electrolytic copper plating, makes evaluation substrate.Cut in copper facing portion the part of width 10mm, long 100mm One end is peeled and is clamped with fixture, measured peel 35mm in vertical direction with the speed of 50mm/ minutes at room temperature by notch When load (peel strength).
[table 36]
* 4-17) curing catalysts 3：Crushing of Ultrafine melamine Misao Kusano manufactures
* 4-18) curing catalysts 4：Dicyandiamide
* 4-19) Photoepolymerizationinitiater initiater 2：907 BASF societies of Irgacure manufacture
* 4-20) photocurable compound 5：Dipentaerythritol tetraacrylate
* 4-21) Thermocurable compound 5：TEPIC-H Misao Kusano manufactures
[table 37]
[table 38]
[table 39]
[table 40]
[table 41]
As described above in detail, by using containing number average fiber diameter for 3nm less than 1000nm's Cellulose nano-fibrous and number average fiber diameter is the insulating materials of 1 μm or more of cellulose fibre, confirms peel strength and flies Improve to jump property.
<Embodiment 5>
[manufacture with the cellulose nano-fibrous dispersion liquid of carboxylate]
(Production Example 1)
By coniferous tree bleached sulfate pulp (Oji Paper's manufacture, the filter of 50 mass % of moisture, Canadian standard Water degree (CSF) 550ml, predominantly number average fiber diameter are more than the absolute dry condition of 1000nm) 5g added in dissolved with 2,2, The aqueous solution 500ml of 6,6- tetramethyl piperidines nitrogen oxides (TEMPO) 79mg (0.5mmol) and sodium bromide 515mg (5mmol) In, it stirs until paper pulp uniformly disperses.The aqueous sodium hypochlorite solution 18ml of effective chlorine 5% is added thereto, with 0.5N hydrochloric acid PH is adjusted to 10 by aqueous solution, starts oxidation reaction.PH is reduced in system in reaction, but gradually addition 0.5N sodium hydroxides are water-soluble PH is adjusted to 10 by liquid.It after reaction 2 hours, is filtered with glass filter, filtrate is fully washed, obtained anti- Answer object.
Then, distilled water is added in into above-mentioned reactant, the aqueous dispersions that pulp density is 2 mass % is made, with rotation Sword formula mixer is dispersed with stirring 5 minutes.With stirring together, the viscosity of slurry significantly rises, thus adds in distillation bit by bit Water continues to be dispersed with stirring until solid component concentration reaches 0.2 mass %, it is water-soluble to obtain transparent gel using mixer Liquid.It is observed using TEM, it is the cellulose nano-fibrous with carboxylate of 10nm to confirm as number average fiber diameter Aqueous dispersions.The amount of the carboxyl of above-mentioned aqueous dispersions is 1.25mmol/g.
It carries out dewatering and filtering to it, adds in the carbitol acetates of 10 times of amounts of filtrate weight, stirring 30 minutes is laggard Row filtering.The replacement operator is repeated 3 times, the carbitol acetate of 10 times of amounts of filtrate weight is added in, makes 10 mass %'s Cellulose nano-fibrous dispersion liquid 1 with carboxylate.
(Production Example 2)
Use 4- dimethylamino -2,2,6,6- tetramethyl piperidines nitrogen oxides (4- dimethylaminos-TEMPO) 100mg (0.5mmol) replaces 2,2,6,6- tetramethyl piperidine nitrogen oxides (TEMPO) 79mg (0.5mmol), in addition to this with manufacture Example 1 similarly makes the cellulose nano-fibrous dispersion liquid 2 with carboxylate of 10 mass %.It should be noted that moisture dissipates The amount of the carboxyl of liquid is 1.30mmol/g, and the cellulose nano-fibrous number average fiber diameter with carboxylate is 12nm.
(Production Example 3)
Carry out generation using 4- carboxyl -2,2,6,6- tetramethyl piperidines nitrogen oxides (4- carboxyls-TEMPO) 101mg (0.5mmol) For 2,2,6,6- tetramethyl piperidine nitrogen oxides (TEMPO) 79mg (0.5mmol), made in the same manner as Production Example 1 in addition to this The cellulose nano-fibrous dispersion liquid 3 with carboxylate of 10 mass %.It should be noted that the amount of the carboxyl of aqueous dispersions is 1.16mmol/g, the cellulose nano-fibrous number average fiber diameter with carboxylate are 10nm.
[manufacture of cellulose nano-fibrous dispersion liquid]
(Production Example 4)
It is crushed using cutting crusher by the plate that timber is process is carried out to eucalyptus, makes the wood of 0.2mm square or so Powder.Then, high temperature high pressure process is carried out to the wood powder in the aqueous solution of sodium sulfite or sodium hydroxide etc., except delignification. It adds in 50 times of distilled water to be stirred, after implementing the mechanical crushing of 15 times using disc mill, in a manner of reaching 10 mass % It adds in distilled water and stirs, it is the cellulose nano-fibrous of 80nm to obtain number average fiber diameter.Dewatering and filtering is carried out to it, is added in The carbitol acetate of 10 times of amounts of filtrate weight, stirring are filtered after 30 minutes.The replacement operator is repeated 3 times, is added in The carbitol acetate of 10 times of amounts of filtrate weight makes the cellulose nano-fibrous dispersion liquid 1 of 10 mass %.
[table 42]
* 5-1) Thermocurable compound 1：828 Mitsubishi chemical Co., Ltd of Epikote manufactures
* 5-2) Thermocurable compound 2：807 Mitsubishi chemical Co., Ltd of Epikote manufactures
* 5-3) curing catalysts 1：2MZ-A Shikoku Chem manufactures
* 5-4) colorant：Phthalocyanine blue
* 5-5) organic solvent：Carbitol acetate
[table 43]
* 5-6) the conjunction object 3 of Thermocurable 1：UNIDIC V-8000 Dainippon Ink Chemicals manufactures (40 mass % of solid constituent)
* 5-7) Thermocurable compound 4：Denacol EX-830 Nagase chemteX Co., Ltd. manufactures
* 5-8) curing catalysts 2：Triphenylphosphine
[table 44]
* 5-9) thermoplastic resin 1：ソ ク シ ー Le SOXR-OB NIPPON KODOSHI CORPORATION are manufactured clear It paints (70 mass % of solid constituent, 30 mass % of N-Methyl pyrrolidone)
[table 45]
* 5-10) photocurable compound 1：Bisphenol-a epoxy acrylate Mitsubishi chemical Co., Ltd manufactures
* 5-11) photocurable compound 2：Trimethylolpropane trimethacrylate
* 5-12) photocurable compound 3：KAYAMER PM2 Nippon Kayaku K. K manufactures
* 5-13) photocurable compound 4：LIGHT ESTER HO Kyoeisha Chemical Co., Ltd. manufactures
* 5-14) Photoepolymerizationinitiater initiater 1：2- ethyl hydrazine
[table 46]
* 5-15) curing catalysts 3：Crushing of Ultrafine melamine Misao Kusano manufactures
* 5-16) curing catalysts 4：Dicyandiamide
* 5-17) Photoepolymerizationinitiater initiater 2：907 BASF systems of Irgacure
* 5-18) photocurable compound 5：Dipentaerythritol tetraacrylate
* 5-19) Thermocurable compound 5：TEPIC-H Misao Kusano manufactures
[table 47]
[table 48]
[making of fracture strength and elongation at break evaluation piece]
According to the record of above-mentioned table 42 come mixture, each ingredient of stirring, make its dispersion with three rollers, make each composition.Then, By silk screen print method by the composition print to thickness be 18 μm copper foil entire surface, using heated air circulation type drying oven with 140 DEG C, the condition of 30 minutes make its curing.Later, copper foil is removed, makes the evaluation piece that thickness is 50 μm.
According to the record of above-mentioned table 43 come mixture, each ingredient of stirring, make its dispersion with three rollers, make each composition.Then, By silk screen print method by the composition print to thickness be 18 μm copper foil entire surface, using heated air circulation type drying oven with 100 DEG C, after the drying of the condition of 30 minutes, its curing is made with the condition of 170 DEG C, 60 minutes.Later, copper foil is removed, makes thickness For 50 μm of evaluation piece.
According to the record of above-mentioned table 44 come mixture, each ingredient of stirring, make its dispersion with three rollers, make each composition.Then, By silk screen print method by the composition print to thickness be 18 μm copper foil entire surface, using heated air circulation type drying oven with 120 DEG C, after the drying of the condition of 10 minutes, its curing is made with the condition of 250 DEG C, 30 minutes.Later, copper foil is removed, makes thickness For 50 μm of evaluation piece.
According to the record of above-mentioned table 45 come mixture, each ingredient of stirring, make its dispersion with three rollers, make each composition.Then, By silk screen print method by the composition print to thickness be 18 μm copper foil entire surface, using metal halide lamp with The wavelength illumination 2J/cm of 350nm2Accumulated light, make its curing.Later, copper foil is removed, the evaluation that thickness is 50 μm is made and uses Piece.
According to the record of above-mentioned 46~table of table 48 come mixture, each ingredient of stirring, make its dispersion with three rollers, make each combination Object.Then, the composition is printed to the entire surface for the copper foil that thickness is 18 μm by silk screen print method, utilizes heated air circulation type Drying oven is 30 minutes dry at 80 DEG C.Then, it using the negative pattern that can cover copper foil central portion, is exposed using use in printed circuit board Ray machine HMW-680GW (ORC Mfg. Co., Ltd.'s manufacture) is with 700mJ/cm2Accumulated light be exposed, by 30 DEG C, 1% Aqueous sodium carbonate as developer solution, developed 60 seconds using use in printed circuit board developing machine, copper foil edge part removed.It connects It, is cured 60 minutes with heated air circulation type drying oven at 150 DEG C.Later, copper foil is removed, makes the evaluation that thickness is 50 μm and use Piece.
[evaluation of fracture strength and elongation at break]
According to JIS K7127, above-mentioned evaluation is cut into certain size with piece, makes test film.For the test film, Fracture strength is measured in 10mm/ minutes with tensile speed using cupping machine (Shimadzu Scisakusho Ltd manufactures AGS-G) After [MPa], elongation at break [%], evaluated based on following evaluation criteria.It the results are shown in following 49~tables of table 52 In.In the evaluation criteria of fracture strength and elongation at break, it is known that：In the case where being zero, the solidfied material tool of test film There is high tenacity, crack resistance is excellent.
(evaluation criteria of fracture strength)
○：More than 75MPa
△：50MPa is less than 75MPa
×：Less than 50MPa
(evaluation criteria of elongation at break)
○：More than 6%
△：4% less than 6%
×：Less than 4%
[making of crack resistance evaluation substrate]
In the making of above-mentioned fracture strength and elongation at break evaluation piece, the FR-4 copper-clads that thickness is 1.6mm are used Pressing plate (copper is 18 μm thick) obtains the solidfied material that film thickness is 20 μm, is produced in addition to this by same process deposited instead of copper foil The evaluation substrate of solidfied material is formed on copper laminated board.
[evaluation of crack resistance]
For above-mentioned evaluation substrate, recycled within 30 minutes, 150 DEG C 30 minutes as 1 using -65 DEG C, provide 1000 and follow The temperature history of ring utilizes the evaluation substrate after light microscope (Co., Ltd. KEYENCE manufactures VHX-2000) observation Crackle and stripping degree, evaluated based on following evaluation criteria.It the results are shown in following 49~tables of table 52.
(evaluation criteria)
○：There is no crackle
△：There is crackle
×：Crackle occurs notable
[table 49]
[table 50]
[table 51]
[table 52]
As described above in detail, it confirms：By using containing with the cellulose nano-fibrous of carboxylate Printed circuit board material can improve crack resistance.
<Embodiment 6>
[manufacture of lignocellulosic nanofiber dispersion liquid]
(Production Example 1)
It is crushed using cutting crusher by the plate that timber is process is carried out to eucalyptus, makes the wood of 0.2mm square or so Powder.Then, 50 times of distilled water of its quality and stirring are added in the wood powder, implements the mechanical crushing of 15 times using disc mill Afterwards, it adds in distilled water in a manner of reaching 10 mass % and stirs, obtain the cellulose Nanowire that number average fiber diameter is 80nm Dimension.Dewatering and filtering is carried out to it, adds in the carbitol acetate of 10 times of amounts of filtrate weight, stirring carried out after 30 minutes Filter.The replacement operator is repeated 3 times, the carbitol acetate of 10 times of amounts of filtrate weight is added in, makes the wooden of 10 mass % Cellulose nano-fibrous dispersion liquid 1.
(Production Example 2)
It is crushed using cutting crusher by the plate that timber is process is carried out to Chinese fir, makes the wood of 0.2mm square or so Powder.Then, 50 times of distilled water of its quality and stirring are added in the wood powder, implements the mechanical crushing of 15 times using disc mill Afterwards, it adds in distilled water in a manner of reaching 10 mass % and stirs, obtain the cellulose Nanowire that number average fiber diameter is 80nm Dimension.Dewatering and filtering is carried out to it, adds in the carbitol acetate of 10 times of amounts of filtrate weight, stirring carried out after 30 minutes Filter.The replacement operator is repeated 3 times, the carbitol acetate of 10 times of amounts of filtrate weight is added in, makes the wooden of 10 mass % Cellulose nano-fibrous dispersion liquid 2.
[comparing the manufacture with cellulose nano-fibrous dispersion liquid]
(Production Example 3)
It is crushed using cutting crusher by the plate that timber is process is carried out to eucalyptus, makes the wood of 0.2mm square or so Powder.Then, high temperature high pressure process is carried out to the wood powder in the aqueous solution of sodium sulfite or sodium hydroxide etc., except delignification. It adds in 50 times of distilled water thereto to be stirred, after implementing the mechanical crushing of 15 times using disc mill, to reach 10 mass % Mode add in distilled water and stir, obtain number average fiber diameter be 80nm it is cellulose nano-fibrous.It is carried out dehydrated Filter, adds in the carbitol acetate of 10 times of amounts of filtrate weight, and stirring is filtered after 30 minutes.It is repeated 3 times displacement behaviour Make, add in the carbitol acetate of 10 times of amounts of filtrate weight, make the cellulose nano-fibrous dispersion liquid 1 of 10 mass %.
[preparation of printed circuit board material]
Record in table 5 below 3, table 54,57~table of table 61 makes its dispersion come mixture, each ingredient of stirring with three rollers, Make each composition.It should be noted that the number in following tables represents mass parts.
Record in table 5 below 5 uses kneading machine (torque rheometer (LABO come each ingredient of mixture PLASTOMILL), Toyo Seiki Co., Ltd. manufactures) at 180 DEG C with rotating speed 70rpm melting mixings 10 minutes.For acquired Mixture, using forcing press (LABOPRESS P2-30T, Toyo Seiki Co., Ltd. manufacture) with 190 DEG C, the item of 0.5MPa Part hot pressing 3 minutes with 20MPa hot pressing 1 minute, and then is suppressed 1 minute with the condition cooling of 23 DEG C, 0.5MPa.As a result, respectively To the cellulose nano-fibrous composite shaped body for the sheet that thickness is 0.5mm and 0.05mm.
Record in table 5 below 6 uses kneading machine (torque rheometer (LABO come each ingredient of mixture PLASTOMILL), Toyo Seiki Co., Ltd. manufactures) at 150 DEG C with rotating speed 70rpm melting mixings 10 minutes.For acquired Mixture, using forcing press (LABOPRESS P2-30T, Toyo Seiki Co., Ltd. manufacture) with 160 DEG C, the item of 0.5MPa Part hot pressing 3 minutes with 20MPa hot pressing 1 minute, and then is suppressed 1 minute with the condition cooling of 23 DEG C, 0.5MPa.As a result, respectively To the cellulose nano-fibrous composite shaped body for the sheet that thickness is 0.5mm and 0.05mm.
[table 53]
* 6-1) Thermocurable compound 1：828 Mitsubishi chemical Co., Ltd of Epikote manufactures
* 6-2) Thermocurable compound 2：807 Mitsubishi chemical Co., Ltd of Epikote manufactures
* 6-3) curing catalysts 1：2MZ-A Shikoku Chem manufactures
* 6-4) pigment：Phthalocyanine blue
* 6-5) organic solvent：Carbitol acetate
[table 54]
* 6-6) Thermocurable compound 3：UNIDIC V-8000 Dainippon Ink Chemicals manufactures (40 mass % of solid constituent)
* 6-7) Thermocurable compound 4：Denacol EX-830 Nagase chemteX Co., Ltd. manufactures
* 6-8) curing catalysts 2：Triphenylphosphine
[table 55]
* 6-9) thermoplastic resin 1：NOVATEC PP BC03L Japan Polypropylene Co., Ltd. manufactures
[table 56]
* 6-10) thermoplastic resin 2：Polyethylene Co., Ltd. of NOVATEC LD LC561 Japan manufactures
[table 57]
* 6-11) thermoplastic resin 3：ソ ク シ ー Le SOXR-OB NIPPON KODOSHI CORPORATION manufactures Varnish (70 mass % of solid constituent, 30 mass % of N-Methyl pyrrolidone)
[table 58]
* 6-12) photocurable compound 1：Bisphenol-a epoxy acrylate Mitsubishi chemical Co., Ltd manufactures
* 6-13) photocurable compound 2：Trimethylolpropane trimethacrylate
* 6-14) photocurable compound 3：KAYAMER PM2 Nippon Kayaku K. K manufactures
* 6-15) photocurable compound 4：LIGHT ESTER HO Kyoeisha Chemical Co., Ltd. manufactures
* 6-16) Photoepolymerizationinitiater initiater 1：2- ethyl hydrazine
[table 59]
* 6-17) curing catalysts 3：Crushing of Ultrafine melamine (Misao Kusano's manufacture)
* 6-18) curing catalysts 4：Dicyandiamide
* 6-19) Photoepolymerizationinitiater initiater 2：Irgacure 907 (manufacture of BASF societies)
* 6-20) photocurable compound 5：Dipentaerythritol tetraacrylate
* 6-21) Thermocurable compound 5：TEPIC-H (Misao Kusano's manufacture)
[table 60]
[table 61]
[evaluation as solder resist]
(making of experiment substrate)
Using the FR-4 copper-coated laminates (copper is 9 μm thick) that size is 100mm × 150mm, thickness is 1.6mm, pass through etching Engineering method makes the comb-type electrode pattern of IPC standard B patterns.
On above-mentioned experiment substrate, silk screen print method printed in a manner of it can cover comb poles embodiment 6-1~ The composition of embodiment 6-6, comparative example 6-1,6-2 make it using heated air circulation type drying oven with the condition of 140 DEG C, 30 minutes Curing, has made test film.
As disruptive test, DC voltage is applied with rate of rise 500V per second to each 6 test films, measures destruction Voltage.The situation of more than the average out to 4.5kV of 6 is evaluated as zero, the situation less than 4.5kV is evaluated as ×.As a result it is as follows： Embodiment 6-1~embodiment 6-6 is zero, and comparative example 6-1,6-2 be ×.
In addition, being tested as insulating reliability, apply the DC voltage of 50V to each 6 test films, in 130 DEG C, 85%RH Atmosphere under carry out placement experiment, measure the time until short circuit.The situation of the average out to 200 hours of 6 or more is evaluated It is zero, the situation less than 200 hours is evaluated as ×.As a result it is as follows：Embodiment 6-1~embodiment 6-6 is zero, comparative example 6- 1st, 6-2 be ×.
On above-mentioned experiment substrate, silk screen print method printed in a manner of it can cover comb poles embodiment 6-7~ The composition of embodiment 6-12, comparative example 6-3,6-4 are dried using heated air circulation type drying oven with the condition of 100 DEG C, 30 minutes Afterwards, its curing is made with the condition of 170 DEG C, 60 minutes, has made test film.
As disruptive test, DC voltage is applied with rate of rise 500V per second to each 6 test films, measures destruction Voltage.The situation of more than the average out to 5.5kV of 6 is evaluated as zero, the situation less than 5.5kV is evaluated as ×.As a result it is as follows： Embodiment 6-7~embodiment 6-12 is zero, and comparative example 6-3,6-4 be ×.
In addition, being tested as insulating reliability, apply the DC voltage of 50V to each 6 test films, in 130 DEG C, 85%RH Atmosphere under carry out placement experiment, measure the time until short circuit.The situation of the average out to 300 hours of 6 or more is evaluated It is zero, the situation less than 300 hours is evaluated as ×.As a result it is as follows：Embodiment 6-7~embodiment 6-12 is zero, comparative example 6-3,6-4 be ×.
On above-mentioned experiment substrate, to embodiment 6-13~embodiment 6-24, ratio in the way of it can cover comb poles The piece that thickness compared with example 6-5~comparative example 6-8 is 0.05mm carries out cutting processing, by hot pressing in 190 DEG C, the condition of 20MPa Lower hot pressing 1 minute, and then cooling compacting 1 minute under conditions of 23 DEG C, 0.5MPa, make test film.
As disruptive test, DC voltage is applied with rate of rise 500V per second to each 6 test films, measures destruction Voltage.The situation of more than the average out to 3.5kV of 6 is evaluated as zero, the situation less than 3.5kV is evaluated as ×.As a result it is as follows： Embodiment 6-13~embodiment 6-24 is zero, and comparative example 6-5~comparative example 6-8 is ×.
In addition, being tested as insulating reliability, apply the DC voltage of 50V to each 6 test films, in 130 DEG C, 85%RH Atmosphere under carry out placement experiment, measure the time until short circuit.The situation of the average out to 250 hours of 6 or more is evaluated It is zero, the situation less than 250 hours is evaluated as ×.As a result it is as follows：Embodiment 6-13~embodiment 6-24 is zero, comparative example 6-5~comparative example 6-8 is ×.
On above-mentioned experiment substrate, silk screen print method printed in a manner of it can cover comb poles embodiment 6-25~ The composition of embodiment 6-30, comparative example 6-9,6-10 are done using heated air circulation type drying oven with the condition of 120 DEG C, 10 minutes After dry, its curing is made with the condition of 250 DEG C, 30 minutes, has made test film.
As disruptive test, DC voltage is applied with rate of rise 500V per second to each 6 test films, measures destruction Voltage.The situation of more than the average out to 5.5kV of 6 is evaluated as zero, the situation less than 5.5kV is evaluated as ×.As a result it is as follows： Embodiment 6-25~embodiment 6-30 is zero, and comparative example 6-9,6-10 be ×.
In addition, being tested as insulating reliability, apply the DC voltage of 50V to each 6 test films, in 130 DEG C, 85%RH Atmosphere under carry out placement experiment, measure the time until short circuit.The situation of the average out to 250 hours of 6 or more is evaluated It is zero, the situation less than 250 hours is evaluated as ×.As a result it is as follows：Embodiment 6-25~embodiment 6-30 is zero, comparative example 6-9,6-10 be ×.
On above-mentioned experiment substrate, silk screen print method printed in a manner of it can cover comb poles embodiment 6-31~ The composition of embodiment 6-36, comparative example 6-11,6-12, then, using metal halide lamp with the wavelength illumination 2J/ of 350nm cm2Accumulated light make its curing, made test film.
As disruptive test, DC voltage is applied with rate of rise 500V per second to each 6 test films, measures destruction Voltage.The situation of more than the average out to 3.5kV of 6 is evaluated as zero, the situation less than 3.5kV is evaluated as ×.As a result it is as follows： Embodiment 6-31~embodiment 6-36 is zero, and comparative example 6-11,6-12 be ×.
In addition, being tested as insulating reliability, apply the DC voltage of 50V to each 6 test films, in 130 DEG C, 85%RH Atmosphere under carry out placement experiment, measure the time until short circuit.The situation of the average out to 100 hours of 6 or more is evaluated It is zero, the situation less than 100 hours is evaluated as ×.As a result it is as follows：Embodiment 6-31~embodiment 6-36 is zero, comparative example 6-11,6-12 be ×.
By silk screen print method, using the 100 inclined versions of mesh polyester by embodiment 6-37~embodiment 6-54, comparative example 6-13~ The composition of comparative example 6-18 is printed to the entire surface on above-mentioned experiment substrate, using heated air circulation type drying oven in 80 DEG C of dryings 30 minutes.Then, using the negative pattern that can cover comb poles, use in printed circuit board exposure machine HMW-680GW (strain formulas are utilized Manufactured by commercial firm ORC makes) with 700mJ/cm2Accumulated light be exposed, using 30 DEG C, 1% aqueous sodium carbonate as Developer solution is developed 60 seconds using use in printed circuit board developing machine, is then carried out 60 minutes with heated air circulation type drying oven at 150 DEG C Heat cure has made test film.
As disruptive test, DC voltage is applied with rate of rise 500V per second to each 6 test films, measures destruction Voltage.The situation of more than the average out to 4.5kV of 6 is evaluated as zero, the situation less than 4.5kV is evaluated as ×.As a result it is as follows： Embodiment 6-37~embodiment 6-54 is zero, and comparative example 6-13~comparative example 6-18 is ×.
In addition, being tested as insulating reliability, apply the DC voltage of 50V to each 6 test films, in 130 DEG C, 85%RH Atmosphere under carry out placement experiment, measure the time until short circuit.The situation of the average out to 200 hours of 6 or more is evaluated It is zero, the situation less than 200 hours is evaluated as ×.As a result it is as follows：Embodiment 6-37~embodiment 6-54 is zero, comparative example 6-13~comparative example 6-18 is ×.
[evaluation as interlayer dielectic]
The composition of embodiment 6-1~embodiment 6-6, comparative example 6-1,6-2 are printed to size by silk screen print method For 100mm × 150mm, the entire surface of FR-4 copper-coated laminates (copper is 9 μm thick) that thickness is 1.6mm, done using heated air circulation type Dry stove makes its curing with the condition of 140 DEG C, 30 minutes.Then, non-electrolytic copper facing is carried out, followed by electrolytic copper plating.Later, The test film of the comb-type electrode pattern with IPC standard B patterns is made by etching engineering method.
As disruptive test, DC voltage is applied with rate of rise 500V per second to each 6 test films, measures destruction Voltage.The situation of more than the average out to 5.5kV of 6 is evaluated as zero, the situation less than 5.5kV is evaluated as ×.As a result it is as follows： Embodiment 6-1~embodiment 6-6 is zero, and comparative example 6-1,6-2 be ×.
In addition, being tested as insulating reliability, apply the DC voltage of 50V to each 6 test films, in 130 DEG C, 85%RH Atmosphere under carry out placement experiment, measure the time until short circuit.The situation of the average out to 400 hours of 6 or more is evaluated It is zero, the situation less than 400 hours is evaluated as ×.As a result it is as follows：Embodiment 6-1~embodiment 6-6 is zero, comparative example 6- 1st, 6-2 be ×.
The composition of embodiment 6-7~embodiment 6-12, comparative example 6-3,6-4 are printed to size by silk screen print method For 100mm × 150mm, the entire surface of FR-4 copper-coated laminates (copper is 9 μm thick) that thickness is 1.6mm, done using heated air circulation type Dry stove with 100 DEG C, after the drying of the condition of 30 minutes, with the condition of 170 DEG C, 60 minutes make its curing.Then, electroless plating is carried out Copper, followed by electrolytic copper plating.Later, the examination of the comb-type electrode pattern with IPC standard B patterns is made by etching engineering method Test piece.
As disruptive test, DC voltage is applied with rate of rise 500V per second to each 6 test films, measures destruction Voltage.The situation of more than the average out to 6.5kV of 6 is evaluated as zero, the situation less than 6.5kV is evaluated as ×.As a result it is as follows： Embodiment 6-7~embodiment 6-12 is zero, and comparative example 6-3,6-4 be ×.
In addition, being tested as insulating reliability, apply the DC voltage of 50V to each 6 test films, in 130 DEG C, 85%RH Atmosphere under carry out placement experiment, measure the time until short circuit.The situation of the average out to 500 hours of 6 or more is evaluated It is zero, the situation less than 500 hours is evaluated as ×.As a result it is as follows：Embodiment 6-7~embodiment 6-12 is zero, comparative example 6-3,6-4 be ×.
For the piece of the thickness 0.05mm of embodiment 6-13~embodiment 6-24, comparative example 6-5~comparative example 6-8, pass through Hot pressing using 190 DEG C, the condition hot pressing of 20MPa to size as 100mm × 150mm, the FR-4 copper-coated laminates that thickness is 1.6mm (copper is 9 μm thick) upper 1 minute, and then suppressed 1 minute with the condition cooling of 23 DEG C, 0.5MPa.Then, non-electrolytic copper facing is carried out, is connect Get off to carry out electrolytic copper plating.Later, the test film of the comb-type electrode pattern with IPC standard B patterns is made by etching engineering method.
As disruptive test, DC voltage is applied with rate of rise 500V per second to each 6 test films, measures destruction Voltage.The situation of more than the average out to 4.5kV of 6 is evaluated as zero, the situation less than 4.5kV is evaluated as ×.As a result it is as follows： Embodiment 6-13~embodiment 6-24 is zero, and comparative example 6-5~comparative example 6-8 is ×.
In addition, being tested as insulating reliability, apply the DC voltage of 50V to each 6 test films, in 130 DEG C, 85%RH Atmosphere under carry out placement experiment, measure the time until short circuit.The situation of the average out to 400 hours of 6 or more is evaluated It is zero, the situation less than 400 hours is evaluated as ×.As a result it is as follows：Embodiment 6-13~embodiment 6-24 is zero, comparative example 6-5~comparative example 6-8 is ×.
The composition of embodiment 6-25~embodiment 6-30, comparative example 6-9,6-10 are printed to big by silk screen print method The entire surface of FR-4 copper-coated laminates (copper is 9 μm thick) that small is 100mm × 150mm, thickness is 1.6mm, utilizes heated air circulation type Drying oven with 120 DEG C, cured after the drying of the condition of 10 minutes, with the condition of 250 DEG C, 30 minutes.Then, non-electrolytic is carried out Copper facing, followed by electrolytic copper plating.Later, the comb-type electrode pattern with IPC standard B patterns is made by etching engineering method Test film.
As disruptive test, DC voltage is applied with rate of rise 500V per second to each 6 test films, measures destruction Voltage.The situation of more than the average out to 6kV of 6 is evaluated as zero, the situation less than 6kV is evaluated as ×.As a result it is as follows：Implement Example 6-25~embodiment 6-30 is zero, and comparative example 6-9,6-10 be ×.
In addition, being tested as insulating reliability, apply the DC voltage of 50V to each 6 test films, in 130 DEG C, 85%RH Atmosphere under carry out placement experiment, measure the time until short circuit.The situation of the average out to 400 hours of 6 or more is evaluated It is zero, the situation less than 400 hours is evaluated as ×.As a result it is as follows：Embodiment 6-25~embodiment 6-30 is zero, comparative example 6-9,6-10 be ×.
By silk screen print method by the composition of embodiment 6-31~embodiment 6-36, comparative example 6-11,6-12 print to The entire surface of FR-4 copper-coated laminates (copper is 9 μm thick) that size is 100mm × 150mm, thickness is 1.6mm, then, utilizes metal Halide lamp is with the wavelength illumination 2J/cm of 350nm2Accumulated light cured.Then, non-electrolytic copper facing is carried out, next Carry out electrolytic copper plating.Later, the test film of the comb-type electrode pattern with IPC standard B patterns is made by etching engineering method.
As disruptive test, DC voltage is applied with rate of rise 500V per second to each 6 test films, measures destruction Voltage.The situation of more than the average out to 4.5kV of 6 is evaluated as zero, the situation less than 4.5kV is evaluated as ×.As a result it is as follows： Embodiment 6-31~embodiment 6-36 is zero, and comparative example 6-11,6-12 be ×.
In addition, being tested as insulating reliability, apply the DC voltage of 50V to each 6 test films, in 130 DEG C, 85%RH Atmosphere under carry out placement experiment, measure the time until short circuit.The situation of the average out to 250 hours of 6 or more is evaluated It is zero, the situation less than 250 hours is evaluated as ×.As a result it is as follows：Embodiment 6-31~embodiment 6-36 is zero, comparative example 6-11,6-12 be ×.
By silk screen print method, using the 100 inclined versions of mesh polyester by embodiment 6-37~embodiment 6-54, comparative example 6-13~ The composition of comparative example 6-18 is printed to FR-4 copper-coated laminates (9 μ of copper thickness that size is 100mm × 150mm, thickness is 1.6mm M) entire surface was made it dry using heated air circulation type drying oven with 80 DEG C, 30 minutes.Then, it is replaced using transparent PET film Negative pattern, using use in printed circuit board exposure machine HMW-680GW (ORC Mfg. Co., Ltd.'s manufacture) with 700mJ/cm2's Accumulated light is exposed, and using 30 DEG C, 1% aqueous sodium carbonate as developer solution, is shown using use in printed circuit board developing machine Shadow 60 seconds then carries out heat cure in 60 minutes at 150 DEG C with heated air circulation type drying oven.Then, non-electrolytic copper facing is carried out, is connect down To carry out electrolytic copper plating.Later, the test film of the comb-type electrode pattern with IPC standard B patterns is made by etching engineering method.
As disruptive test, DC voltage is applied with rate of rise 500V per second to each 6 test films, measures destruction Voltage.The situation of more than the average out to 5.5kV of 6 is evaluated as zero, the situation less than 5.5kV is evaluated as ×.As a result it is as follows： Embodiment 6-37~embodiment 6-54 is zero, and comparative example 6-13~comparative example 6-18 is ×.
In addition, being tested as insulating reliability, apply the DC voltage of 50V to each 6 test films, in 130 DEG C, 85%RH Atmosphere under carry out placement experiment, measure the time until short circuit.The situation of the average out to 400 hours of 6 or more is evaluated It is zero, the situation less than 400 hours is evaluated as ×.As a result it is as follows：Embodiment 6-37~embodiment 6-54 is zero, comparative example 6-13~comparative example 6-18 is ×.
[evaluation as core material]
(making of lignocellulosic nanofiber piece)
About lignocellulosic nanofiber dispersion liquid 1 and lignocellulosic nanofiber dispersion liquid 2, carbitol second is utilized Acid esters makes 0.2 mass % dispersion liquids, is filtered using glass filter, making size is 100mm × 150mm, thickness is 40 μm of piece.
(making of cellulose nano-fibrous)
About cellulose nano-fibrous dispersion liquid 1,0.2 mass % dispersion liquids are made using carbitol acetate, utilize glass Glass filter is filtered, the piece that making size is 100mm × 150mm, thickness is 40 μm.
828 50 mass parts of Epikote of Mitsubishi chemical Co., Ltd's manufacture, Mitsubishi chemical Co., Ltd are manufactured 807 50 mass parts of Epikote, 3 mass parts of 2MZ-A, 100 matter of methyl ethyl ketone of Shikoku Chem's manufacture It measures part and carries out mixture, stirring, obtain resin solution.Each cellulose nano-fibrous is allowed to penetrate into, is placed under 50 DEG C of atmosphere It is taken out after 12 hours, it is 5 hours dry at 80 DEG C, make prepreg.10 prepregs are overlapped, and then the overlapped thickness in table For 18 μm of copper foil, cured 3 hours with 160 DEG C of temperature, the condition of pressure 2MPa using vacuum press.Later, pass through etching Engineering method makes the test film of the comb-type electrode pattern with IPC standard B patterns.By lignocellulosic nanofiber dispersion liquid 1 Test film is as embodiment 6-55, using the test film of lignocellulosic nanofiber dispersion liquid 2 as embodiment 6-56, by fiber The test film of plain nanofiber dispersion liquid 1 as comparative example 6-19, and then will use glass cloth replace it is cellulose nano-fibrous and The test film equally made is as comparative example 6-20.Embodiment 6-55, embodiment 6-56, comparative example 6-19, comparative example 6-20 The filling rate of cellulose fibre is 30 mass %.It should be noted that in embodiment 6-55, embodiment 6-56, third is added Olefin(e) acid system copolymerization (manufacture of BYK-361N BYK-CHEMIE Japan Co., Ltd.) 1 mass parts.
As disruptive test, DC voltage is applied with rate of rise 500V per second to each 6 test films, measures destruction Voltage.The situation of more than the average out to 5.5kV of 6 is evaluated as zero, the situation less than 5.5kV is evaluated as ×.As a result it is as follows： Embodiment 6-55,6-56 is zero, and comparative example 6-19,6-20 be ×.
In addition, being tested as insulating reliability, apply the DC voltage of 50V to each 6 test films, in 130 DEG C, 85%RH Atmosphere under carry out placement experiment, measure the time until short circuit.The situation of the average out to 400 hours of 6 or more is evaluated It is zero, the situation less than 400 hours is evaluated as ×.As a result it is as follows：Embodiment 6-55,6-56 is zero, comparative example 6-19,6- 20 be ×.
By 100 mass parts of UNIDIC V-8000 of Dainippon Ink Chemicals's manufacture, the manufacture of Nagase chemteX Co., Ltd. 23 mass parts of Denacol EX-830,1 mass parts of triphenylphosphine, 100 mass parts of methyl ethyl ketone carry out mixture, stirring, obtain To resin solution.Each cellulose nano-fibrous is allowed to penetrate into, is taken out after being placed 12 hours under 50 DEG C of atmosphere, it is dry at 80 DEG C Dry 5 hours, make prepreg.10 prepregs are overlapped, and then 18 μm of copper foil is overlapped in table, utilize vacuum press Cured 3 hours with 160 DEG C of temperature, the condition of pressure 2MPa.Later, the comb with IPC standard B patterns is made by etching engineering method The test film of type electrode pattern.Using the test film of lignocellulosic nanofiber dispersion liquid 1 as embodiment 6-57, by wooden fibre The test film of the plain nanofiber dispersion liquid 2 of dimension as embodiment 6-58, using the test film of cellulose nano-fibrous dispersion liquid 1 as Comparative example 6-21, and then the test film that glass cloth equally makes instead of cellulose nano-fibrous will be used as comparative example 6- 22.Embodiment 6-57, embodiment 6-58, comparative example 6-21, comparative example 6-22 cellulose fibre filling rate be 30 mass %. It should be noted that in embodiment 6-57, embodiment 6-58, acrylic copolymer compound (BYK-361N BYK- are added CHEMIE Japan Co., Ltd. manufactures) 1 mass parts.
As disruptive test, DC voltage is applied with rate of rise 500V per second to each 6 test films, measures destruction Voltage.The situation of more than the average out to 6.5kV of 6 is evaluated as zero, the situation less than 6.5kV is evaluated as ×.As a result it is as follows： Embodiment 6-57,6-58 is zero, and comparative example 6-21,6-22 be ×.
In addition, being tested as insulating reliability, apply the DC voltage of 50V to each 6 test films, in 130 DEG C, 85%RH Atmosphere under carry out placement experiment, measure the time until short circuit.The situation of the average out to 500 hours of 6 or more is evaluated It is zero, the situation less than 500 hours is evaluated as ×.As a result it is as follows：Embodiment 6-57,6-58 is zero, comparative example 6-21,6- 22 be ×.
By 100 mass parts of ソ ク シ ー Le SOXR-OB of NIPPON KODOSHI CORPORATION manufactures, methyl second 70 mass parts of base ketone carry out mixture, stirring, obtain resin solution.Each cellulose nano-fibrous is allowed to penetrate into, in 50 DEG C of gas It is taken out after being placed 12 hours under atmosphere, it is 5 hours dry at 80 DEG C, make prepreg.10 prepregs are overlapped, and then in table The copper foil of 18 μm of overlapping is cured 3 hours using vacuum press with 160 DEG C of temperature, the condition of pressure 2MPa.Later, pass through erosion Carve the test film that engineering method makes the comb-type electrode pattern with IPC standard B patterns.By lignocellulosic nanofiber dispersion liquid 1 Test film as embodiment 6-59, will be fine using the test film of lignocellulosic nanofiber dispersion liquid 2 as embodiment 6-60 The test film of the plain nanofiber dispersion liquid 1 of dimension is as comparative example 6-23, and then it is cellulose nano-fibrous that glass cloth will be used to replace And the test film equally made is as comparative example 6-24.Embodiment 6-59, embodiment 6-60, comparative example 6-23, comparative example 6-24 Cellulose fibre filling rate be 30 mass %.It should be noted that in embodiment 6-59, embodiment 6-60, add Acrylic copolymer compound (manufacture of BYK-361N BYK-CHEMIE Japan Co., Ltd.) 1 mass parts.
As disruptive test, DC voltage is applied with rate of rise 500V per second to each 6 test films, measures destruction Voltage.The situation of more than the average out to 6kV of 6 is evaluated as zero, the situation less than 6kV is evaluated as ×.As a result it is as follows：Implement Example 6-59,6-60 are zero, and comparative example 6-23,6-24 be ×.
In addition, being tested as insulating reliability, apply the DC voltage of 50V to each 6 test films, in 130 DEG C, 85%RH Atmosphere under carry out placement experiment, measure the time until short circuit.The situation of the average out to 400 hours of 6 or more is evaluated It is zero, the situation less than 400 hours is evaluated as ×.As a result it is as follows：Embodiment 6-59,6-60 is zero, comparative example 6-23,6- 24 be ×.
In embodiment 6-13~embodiment 6-24, the table inner layer of the piece of the thickness 0.5mm of comparative example 6-5~comparative example 6-8 Copper foil 18 μm folded is heated 1 minute using vacuum press with 190 DEG C of temperature, the condition of pressure 0.5MPa.Later, pass through erosion Carve the test film that engineering method makes the comb-type electrode pattern with IPC standard B patterns.
As disruptive test, DC voltage is applied with rate of rise 500V per second to each 6 test films, measures destruction Voltage.The situation of more than the average out to 4.5kV of 6 is evaluated as zero, the situation less than 4.5kV is evaluated as ×.As a result it is as follows： Embodiment 6-13~embodiment 6-24 is zero, and comparative example 6-5~comparative example 6-8 is ×.
In addition, being tested as insulating reliability, apply the DC voltage of 50V to each 6 test films, in 130 DEG C, 85%RH Atmosphere under carry out placement experiment, measure the time until short circuit.The situation of the average out to 400 hours of 6 or more is evaluated It is zero, the situation less than 400 hours is evaluated as ×.As a result it is as follows：Embodiment 6-13~embodiment 6-24 is zero, comparative example 6-5~comparative example 6-8 is ×.
As described above in detail, it confirms：By using containing the cellulose nanometer manufactured by lignocellulosic The printed circuit board material of fiber, so as to can realize the raising of proof voltage and insulating reliability that can not be realized in the past.
The explanation of symbol
1st, 3,8,11 conductive pattern
2 core substrates
1a, 4 connecting portions
5 through-holes
6th, 9 interlayer insulating film
7th, 10 via hole
12 solder mask layers
13 copper-coated laminates (experiment substrate)
13a conductor layers
13b insulating layers
14 insulating resin layers
15 laser via holes
16 coating layers
17 corrosion-resisting patterns
18 Wiring patterns
21 copper-coated laminates (experiment substrate)
21a conductor layers
21b insulating layers
22 insulating resin layers
23 laser via holes
24 coating layers
25 corrosion-resisting patterns
26 Wiring patterns
27 through holes
28 through-holes

Claims (10)

1. a kind of printed circuit board material, which is characterized in that it includes Binder Composition, by there is carboxylic in the C6 positions of structural unit The number average fiber diameter that cellulosic molecule that the content of hydrochlorate and carboxyl is 0.1mmol/g~3mmol/g is formed be 3nm~ The cellulose nano-fibrous and acrylic copolymer compound of 1000nm.
2. printed circuit board material as described in claim 1, wherein, the Binder Composition is thermoplastic resin.
3. printed circuit board material as described in claim 1, wherein, the Binder Composition is curable resin.
4. printed circuit board material as described in claim 1, it includes phyllosilicates.
5. printed circuit board material as described in claim 1, it includes any one in organo-silicon compound and fluorine compounds Person or both.
6. printed circuit board material as described in claim 1, wherein, the cellulose nano-fibrous number average fiber diameter is For 3nm less than 1000nm, which further includes the cellulose fiber that number average fiber diameter is 1 μm or more Dimension.
7. printed circuit board material as described in claim 1, wherein, it is described cellulose nano-fibrous by lignocellulosic system It makes.
8. printed circuit board material as described in claim 1, is used for solder resist.
9. printed circuit board material as described in claim 1 is used for the interlayer dielectic of multilayer board.
10. a kind of printed circuit board, which is characterized in that it uses printed circuit boards according to any one of claims 1 to 9 Material.
CN201480018767.5A 2013-04-23 2014-04-22 Printed circuit board material and the printed circuit board for having used the material Active CN105122953B (en)

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JP3050276U (en) * 1997-12-27 1998-06-30 イビデン株式会社 Printed wiring board
JP4107394B2 (en) * 2005-09-15 2008-06-25 積水化学工業株式会社 Resin composition, sheet-like molded body, prepreg, cured body, laminated board, and multilayer laminated board

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WO2014175244A1 (en) 2014-10-30
TW201513742A (en) 2015-04-01

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