CN105073416B - Light sintering thermoplastic resin membrane base material, conducting channel substrate and its manufacture method using it - Google Patents
Light sintering thermoplastic resin membrane base material, conducting channel substrate and its manufacture method using it Download PDFInfo
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- CN105073416B CN105073416B CN201480019404.3A CN201480019404A CN105073416B CN 105073416 B CN105073416 B CN 105073416B CN 201480019404 A CN201480019404 A CN 201480019404A CN 105073416 B CN105073416 B CN 105073416B
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- base material
- resin
- circuit pattern
- conducting channel
- channel substrate
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
-
- 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
- H05K1/036—Multilayers with layers of different types
-
- 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
- H05K1/0393—Flexible 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
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/12—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns
- H05K3/1283—After-treatment of the printed patterns, e.g. sintering or curing methods
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/08—PCBs, i.e. printed circuit boards
-
- 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
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/01—Dielectrics
- H05K2201/0104—Properties and characteristics in general
- H05K2201/0129—Thermoplastic polymer, e.g. auto-adhesive layer; Shaping of thermoplastic polymer
-
- 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
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/01—Dielectrics
- H05K2201/0183—Dielectric layers
- H05K2201/0195—Dielectric or adhesive layers comprising a plurality of layers, e.g. in a multilayer structure
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- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Manufacturing Of Printed Wiring (AREA)
- Laminated Bodies (AREA)
Abstract
There is provided will not also make the circuit pattern for being formed at surface produce broken string, the light sintering thermoplastic resin membrane base material of crackle, conducting channel substrate and its manufacture method using it even if progress light sintering.A kind of smooth sintering thermoplastic resin membrane base material, it is on the top layer of base material (1) formed with the resin bed (5) with cross-linked structure.In addition, conducting channel substrate on above-mentioned smooth sintering thermoplastic resin membrane base material formed with circuit pattern.And then the manufacture method of conducting channel substrate forms circuit pattern on above-mentioned smooth sintering thermoplastic resin membrane base material, light sintering then is carried out to circuit pattern.
Description
Technical field
The present invention relates to light sintering thermoplastic resin membrane base material (following, to be also referred to simply as " base material "), conducting channel
The manufacture method of substrate and conducting channel substrate, specifically, being related to will not also make to be formed at surface even if progress light sintering
Circuit pattern produces broken string, the light sintering thermoplastic resin membrane base material of crackle, using its conducting channel substrate and its system
Make method.
Background technology
At present, by the way that the conductive resin composition of thermohardening type is coated with or printed on film substrate, glass substrate etc.,
And it is heating and curing, so as to form circuit pattern of the electrode of resistive film mode touch panel, printed circuit board (PCB) etc..Separately
Outside, it is general using containing very big for the formation of the conductive pattern in plasma display panel, fluorescent display tube, electronic unit etc.
The metal powder of amount or the conductive paste of glass powder are formed by silk screen print method to carry out pattern.
However, it is necessary to heating under high temperature, sintering in such method, therefore substrate be present and be defined to not by high temperature
This difficult point of the material of influence.For example, cellulose (paper), polyethylene terephthalate (PET), polyester and other many
The lower or flexible substrate of the cost of plastics etc. can not be resistant to the temperature of these methods mostly.Similarly, organic semiconductor be present
The worry that can be also decomposed at high temperature Deng the other compositions on substrate.
As solving the problems, such as such means, in recent years, so-called light sinters this technology and developed, and attracts attention.
For example, following method is proposed in patent document 1：By the dispersion at least containing nano particle of the particle diameter less than 1 μm in base material
Upper carry out pattern printing, radiation pulses light, so as to which a part of nano particle comprising most metal nanoparticle can be with
The behavior embodied as black matrix is said, shows high electromagnetic radiation absorptivity, and the thermal mass of particle is small, so as to form particle
The circuit pattern for drastically heating, fusing and solidify.In the case of this method, the thermal conductivity factor of substrate is poor, and pulse length
It is short, therefore be only capable of transmitting minimal energy to substrate, so as to solve the existing method based on heat cure, sintering
Problem.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Application Publication 2008-522369 publications
The content of the invention
Problems to be solved by the invention
However, form circuit diagram in the flexible substrates such as plastics using such light sintering technology described in patent document 1
During case, flexible substrate sustains damage in sintering and causes circuit pattern to crack, break sometimes.Therefore, at present, light is utilized
This technology is sintered when forming circuit pattern in the flexible substrates such as plastics, it is necessary to solve the problems, such as such.
Therefore, it is an object of the present invention to provide will not also make the circuit pattern that is formed at surface even if carrying out light sintering
Produce broken string, the light sintering thermoplastic resin membrane base material of crackle, conducting channel substrate and its manufacture method using it.
The solution used to solve the problem
The present inventor has made intensive studies to eliminate above mentioned problem, as a result obtains following discovery.Fig. 5 is existing
Light when circuit pattern is formed on base material sinters the sectional view of front and rear base material, and (a) is before light sinters, and (b) is after light sinters.
When circuit pattern is formed in the flexible substrates such as plastics 1, to the film of the circuit pattern formed by conductive composition on base material 1
During 2 progress light sintering, the particle of the conductive material in conductive composition is drastically heated, fused and solidifies on base material 1, shape
Into the conductor 3 corresponding with circuit pattern.Now, conductor 3 simultaneously because heat and shrink.On the other hand, with the temperature of conductor 3
Rise, the temperature of base material 1 also rises, therefore in the case of the flexible substrate 1 such as use plastics, the temperature of base material 1 rises to fusing point
During the above, with the contraction of conductor 3, base material 1 itself can also shrink.
In illustrated example, the base material 1 near the edge part of conductor 3 is stretched with the contraction of conductor 3, so as to produce depression 4,
Base material 1 sustains damage.Thus, it is possible to think that the circuit pattern for being formed at flexible substrate 1 can produce broken string.The present inventor is based on upper
Discovery is stated, is further furtherd investigate, is as a result found：By setting the resin bed with cross-linked structure on the top layer of base material,
It can solve the above problems, so as to complete the present invention.
That is, light sintering thermoplastic resin membrane's base material of the invention is characterised by, on the top layer of base material formed with tool
The resin bed of crosslinking structure.Herein, cross-linked structure refers to, between the identical macromolecule with crosslinked group, xenogenesis high score
Between son, between macromolecule-low molecule between identical or xenogenesis low molecule, bonded together by electromagnetic energy such as heat, light etc.
And formed, three-dimensional network structure.Disappeared by forming possessed by cross-linked structure, macromolecule etc. fusing point, it is apparent on point
Son amount becomes infinitely great, therefore is changed in terms of mobility, solubility, and shows chemical proofing, solvent resistance, resistance to
The excellent characteristic such as Hou Xing, heat resistance, heat-resistant aging.It should be noted that the glass transition temperature shown in this specification
Degree can be determined by known conventional assay method, and (DSC is determined preferably by Differential Scanning Calorimetry：
Differential scanning calorimetry) and determine obtained value.
In the film substrate of the present invention, it is preferred that aforementioned resin layer is solidified by irradiating active energy beam
Obtained from.
In addition, the conducting channel substrate of the present invention is characterised by, in the light sintering thermoplastic resin of the invention described above
Formed with circuit pattern on film substrate.
And then the manufacture method of conducting channel substrate of the invention is characterised by, it is electric for the conduction of the invention described above
The manufacture method of base board, circuit pattern is formed on foregoing smooth sintering thermoplastic resin membrane base material, then to the circuit
Pattern carries out light sintering.
The effect of invention
Break according to the present invention it is possible to provide and even if progress light sintering the circuit pattern for being formed at surface will not also produced
Line, the light sintering thermoplastic resin membrane base material of crackle, conducting channel substrate and its manufacture method using it.
Brief description of the drawings
Fig. 1 is the sectional view of the front and rear base material of the light sintering when forming circuit pattern on the base material of the present invention, and (a) is light
Before sintering, (b) is after light sinters.
Fig. 2 is the electron micrograph of a part for the circuit pattern of the conducting channel substrate of embodiment 1.
Fig. 3 is the electron micrograph of a part for the circuit pattern of the conducting channel substrate of reference example.
Fig. 4 is the electron micrograph of a part for the circuit pattern of the conducting channel substrate of comparative example.
Fig. 5 is the sectional view of the front and rear base material of the existing light sintering when forming circuit pattern on base material, and (a) burns for light
Before knot, (b) is after light sinters.
Embodiment
Hereinafter, embodiments of the present invention are described in detail.
[light sintering thermoplastic resin membrane base material]
For light sintering thermoplastic resin membrane's base material of the present invention, on the top layer of base material formed with cross-linked structure
Resin bed.Fig. 1 is the sectional view of the front and rear base material of the light sintering when forming circuit pattern on the base material of the present invention, and (a) is
Before light sintering, (b) is after light sinters.As illustrated, for the base material of the present invention, being set on the top layer of base material 1 has crosslinking
The resin bed 5 of structure.By the resin bed 5, even if conductor 3 shrinks when light sinters, base material 1 will not also shrink, and can prevent light
Crackle, the broken string of circuit pattern during sintering.In order to obtain the effect above well, what is formed on base material top layer has crosslinking knot
The glass transition temperature of the resin bed of structure is preferably more than 100 DEG C, more preferably more than 140 DEG C and less than 250 DEG C.
In the base material of the present invention, the resin bed 5 on the surface for being arranged at base material 1, as long as there is cross-linked structure, preferably glass
Glass transition temperature meets above range, is just not particularly limited, and is preferably solidified by irradiating active energy beam to obtain
Arrive.This is because, coating carries out active energy beam irradiation to it and made as the resin combination of resin bed 5 on base material 1
It solidifies, so as to be readily formed the resin bed 5 with cross-linked structure.
As described above, the resin combination of the resin bed 5 as the base material for forming the present invention, as long as in the shape of resin bed 5
There is cross-linked structure under state, be just not particularly limited, however, the resin combination of the resin bed 5 as the base material for forming the present invention
Thing, preferably actinic energy ray curable resion composition, as active energy ray-curable resin, have in a preferably molecule
There is the compound of more than one ethylenic unsaturated bond.Such as it can enumerate：Epoxy (methyl) acrylate, carbamate propylene
Acid esters, polyester acrylate, polyether acrylate, in the side chain of acrylic resin the modifications of ethylenical unsaturated double bonds is imported
Acrylic resin etc..Wherein, the compound more preferably with more than two ethylenic unsaturated bonds, and then particularly preferably benzene diformazan
Diallyl phthalate resin.The resin combination for forming the resin bed 5 of the base material of the present invention contains：(A) dially phthalate
Resin, (B) polyfunctional monomer and (C) Photoepolymerizationinitiater initiater.Hereinafter, to more with (A) dially phthalate resin, (B)
The resin combination of functional monomer and (C) Photoepolymerizationinitiater initiater is described in detail.
It should be noted that in this specification, (methyl) acrylate refer to be referred to as acrylate, methacrylate and
The term of their mixture, for other similar expression similarly.
＜ (A) dially phthalate resin ＞
Formed in the resin combination of the resin bed 5 of the base material of the present invention, as dially phthalate resin, as long as
Comprising dially phthalate system repeat unit, can be dially phthalate system monomer homopolymer, 2 kinds with
On dially phthalate system monomer copolymer and dially phthalate system monomer with can be total to the monomer
Poly- other monomers are (for example, the aromatic compound with olefinic double bond, the aliphatic compound with olefinic double bond or (first
Base) acrylic compounds) copolymer.Dially phthalate system monomer with can be with the other monomers of the monomer copolymerization
Copolymer generally using dially phthalate system repeat unit as main body.
Dially phthalate system monomer as the raw material of dially phthalate resin is selected from O-phthalic
Compound in diallyl phthalate monomer, DAIP monomer and diallyl p phthalate monomer.Use
The synthesis of the dially phthalate resin of these one kind or two or more compounds and use these dially phthalates
Be monomer with can be with gimmick known to the synthesis use of the dially phthalate resin for the other monomers that the monomer polymerize
, such as can use described in Japanese Patent Publication 2-024850 publications, Japanese Unexamined Patent Publication 11-147917 publications etc.
Polymerisation.
The dially phthalate tree used in resin combination as the resin bed 5 for the base material for forming the present invention
Fat, for example, " DAP-A " (registration mark) of preferred DAISO CO., LTD. manufacture it is such, belong to the phthalic acid two of homopolymer
Allyl ester resin, DAISO CO., " ISODAP " (registration mark) of LTD. manufactures is such, DAIP tree
Fat, diallyl p phthalate resin, more preferably diallyl phthalate resin and DAIP tree
Fat.
Formed in the resin combination of the resin bed 5 of the base material of the present invention, the allyl of phthalic acid two used can be adapted to
Ester resin using GPC (gel permeation chromatography) measure weight average molecular weight (polystyrene conversion) be 20000~60000,
More preferably 50000~60000.This is because, when weight average molecular weight is more than 60000, there is the worry of curability variation, be less than
When 20000, there is the worry that heat resistance is deteriorated.
＜ (B) polyfunctional monomers ＞
Formed in the resin combination of the resin bed 5 of the base material of the present invention, as polyfunctional monomer, as long as in 1 molecule
At least there is the compound of more than 2 polymerism unsaturated groups, it is possible to use any monomer.Specifically, can be preferred
Enumerate on ground：Compound obtained from polyalcohol is condensed with alpha, beta-unsaturated carboxylic acid (such as ethylene glycol two (methyl) acrylate (table
Show diacrylate or dimethylacrylate, following same), triethylene glycol two (methyl) acrylate, (the first of tetraethylene glycol two
Base) acrylate, the acrylate of dihydroxy methylpropane six, trimethylolpropane two (methyl) acrylate, trimethylolpropane
Three (methyl) acrylate, 1,2- propane diols two (methyl) acrylate, two (1,2- propane diols) two (methyl) acrylate, three
(1,2- propane diols) two (methyl) acrylate, four (1,2- propane diols) two (methyl) acrylate, (methyl) acrylic acid diformazan
Base amino ethyl ester, (methyl) acrylic acid diethylamino ethyl ester, (methyl) acrylate propyl ester, (methyl) acrylic acid
Diethylamino propyl ester, 1,4- butanediols two (methyl) acrylate, 1,6-HD two (methyl) acrylate, pentaerythrite
Three (methyl) acrylate etc.), styrene, divinylbenzene, 4- vinyltoluenes, 4-vinylpridine, N- vinyl pyrroles
Alkanone, (methyl) acrylic acid 2- hydroxy methacrylates, 1,3- (methyl) acryloxy -2- hydroxy propanes, methylene-bisacrylamide,
N, N- DMAA, N hydroxymethyl acrylamide, neopentyl glycol two (methyl) acrylate, pentaerythrite two (methyl)
Acrylate, dipentaerythritol six (methyl) acrylate, tetra methylol propane four (methyl) acrylate etc., more preferably dihydroxy
The acrylate of methylpropane six, trimethylolpropane tris (methyl) acrylate, pentaerythrite three (methyl) acrylate, two seasons
Monomers more than 3 functions such as penta tetrol six (methyl) acrylate, tetra methylol propane four (methyl) acrylate.Form this hair
In the resin combination of the resin bed 5 of bright base material, they can use a kind or combine two or more use.
Formed in the resin combination of the resin bed 5 of the base material of the present invention, polyfunctional monomer is relative to phthalic acid diene
The mass parts of propyl ester resin 100 are preferably compounded with the ratio of 1~100 mass parts, the scope of further preferred 3~50 mass parts.Partially
From 1~100 mass parts scope when, can not obtain sometimes the present invention intended effect, not preferably.
＜ (C) Photoepolymerizationinitiater initiaters ＞
Formed in the resin combination of the resin bed 5 of the base material of the present invention, as Photoepolymerizationinitiater initiater, can use pass through
Irradiate active energy beam and produce the known compound of free radical, such as can enumerate：Acetophenone, 2,2- dimethoxys -2-
Phenyl acetophenone, 2,2- diethoxy -2- phenyl acetophenones, to dimethylamino propiophenone, dichloroacetophenone, trichloro-benzenes second
Ketone, to tert-butyl group trichloroacetophenone, 1- hydroxy cyclohexyl phenylketones, 2- methyl isophthalic acids-[4- (methyl mercapto) phenyl] -2- morpholinyls -
1- acetone, 2- benzyl -2- dimethylaminos -1- (4- morpholino phenyls) -1- butanone, the benzene second such as N, N- dimethylamino benzoylformaldoximes
Ketone；Benzophenone, methyl benzophenone, 2- chlorobenzophenones, 4,4 '-dichloro benzophenone, 4,4 '-bis- dimethylaminos two
The benzophenone such as Benzophenone, 4,4 '-bis- diethylamino benzophenone, Michler's keton, 4- benzoyls -4 '-methyldiphenyl thioether
Class；The benzoin ethers such as benzil, benzoin, benzoin methylether, benzoin ethyl ether, benzoin iso-propylether, benzoin isobutyl ether；
The ketal class such as acetophenone dimethyl ketal, benzil dimethyl ketal；Thioxanthones, CTX, 2,4- dimethyl thioxanthones,
The thioxanthene ketone class such as 2,4- diethyl thioxanthones, 2,4- diisopropylthioxanthones；2-methylanthraquinone, 2- EAQs, the 2- tert-butyl groups
The Anthraquinones such as anthraquinone, 1- chloroanthraquinones, 2- amino anthraquinones, 2,3- diphenyl anthraquinones；Benzoyl peroxide, cumene peroxide etc. are organic
Peroxide；2,4,5- triarylimidazoles dimer, Riboflavin Tetrabutyrate, 2-mercaptobenzimidazole, 2- mercaptobenzoxazoles,
The mercaptan compounds such as 2-mercaptobenzothiazole；The s-triazine of 2,4,6- tri-, 2,2,2- ethobroms, trisbromomethyl phenyl sulfone etc. are organic
Halogen compounds；2,4,6- trimethyl benzoyl diphenyl base phosphine oxides etc..In addition, as other examples, can enumerate：Acridine
Compounds, oxime esters etc..Formed in the resin combination of the resin bed 5 of the base material of the present invention, they can use a kind or group
Close two or more use.
Formed in the resin combination of the resin bed 5 of the base material of the present invention, Photoepolymerizationinitiater initiater as described above can be with
N, N- dimethyl amino benzoate, N, N- dimethylaminobenzoic acids isopentyl ester, 4- dimethylaminobenzoic acids pentyl ester, three
The thioether such as the tertiary amines such as ethamine, triethanolamine and β-thiodiglycol class, (ketone) cumarin, thioxanthene etc. are sensitized pigment and flower
Photosensitizer as the alkyl borates such as green grass or young crops, rhodamine, sarranine, peacock green, methylene blue or a kind in accelerator or 2 kinds
Combination of the above uses.
As the preferred compositions of Photoepolymerizationinitiater initiater, can enumerate：2- methyl isophthalic acids-[4- (methyl mercapto) phenyl] -2- morpholines
Base -1- acetone (such as BASF Japan Ltd. manufacture, IRGACURE 907) and CTX (such as Japanese chemical drug strain formula
Commercial firm manufacture KAYACURE CTX), 2,4- diethyl thioxanthones (such as Nippon Kayaku K. K manufacture KAYACURE
DETX), the combination of ITX, 4- benzoyls -4 '-dimethyl diphenyl sulfide etc..
Formed in the resin combination of the resin bed 5 of the base material of the present invention, the suitable model of the addition of Photoepolymerizationinitiater initiater
It is 0.01~30 mass parts, preferably 0.1~20 mass parts to enclose relative to the mass parts of dially phthalate resin 100.Light
When the compounding ratio of polymerization initiator is less than 0.01 mass parts, photo-curable is deteriorated, on the other hand, during more than 30 mass parts, Gu
The characteristic for changing film is deteriorated, and storage stability is deteriorated, and it is not preferable.
Other additives of ＜ ＞
Formed in the resin combination of the resin bed 5 of the base material of the present invention, in addition to above-mentioned (A)~(C), as long as not damaging
The intended effect of the evil present invention, can also add other additives.As additive, such as can enumerate：Silicon-type, fluorine
The defoamer of system, levelling agent, known conventional thermal polymerization inhibitor, ultra-violet absorber, silane coupler, plasticizer, foaming
Agent, fire retardant, antistatic additive, age resistor, antibacterial/mould inhibitor etc..
＜ fillers ＞
The inorganic or organic filler that the resin bed 5 of the base material of the present invention can be commonly used known in, particularly preferred barium sulfate,
Spherical silicon dioxide, the average primary particle diameter of spherical silicon dioxide is preferably 1~100nm.Herein, average primary particle diameter refers to,
Pass through the value of laser scattering method.Specifically, the average grain diameter to obtain as follows：Nano silicon is scattered in solvent
In, catch to scattering light obtained from dispersion solvent irradiation laser, and calculate, the average grain diameter obtained from.Nanometer
Silica can use and implement the nano silicon of surface treatment, untreated nano-silica using silane coupler etc.
Any of SiClx.Alternatively, it is also possible to use：In the compound with more than 2 ethylenically unsaturated groups, multi-functional epoxy
NANOCRYL (trade name) XP 0396, the XP of the Hanse-Chemie companies manufacture of nano silicon are dispersed with resin
0596th, XP 0733, XP 0746, XP 0765, XP 0768, XP 0953, XP 0954, XP 1045 (being product hierarchy name),
NANOPOX (trade name) XP 0516, XP 0525, the XP 0314 (being product hierarchy name) of Hanse-Chemie companies manufacture.
These fillers can individually be compounded or be compounded two or more.These fillers can suppress the cure shrinkage of film, improve adaptation,
The fundamental characteristics such as hardness.
In the resin bed 5 of the base material of the present invention, the compounding amount of these fillers is relative to (A) dially phthalate resin
100 mass parts are preferably 0.1~300 mass parts, more preferably 0.1~150 mass parts.The compounding amount of filler is less than 0.1 mass
During part, cured coating film characteristic reduces, and it is not preferable.When on the other hand, more than 300 mass parts, the viscosity of composition uprises, printing
Property reduce, or solidfied material becomes fragile, and it is not preferable.
＜ organic solvents ＞
Formed in the resin combination of the resin bed 5 of the base material of the present invention, according to need in order to making resin combination uniform
Dissolving or adjustment viscosity, can also use organic solvent.As long as organic solvent can by each composition uniform dissolution and not with respectively
Composition reacts, and is just not particularly limited.
As these organic solvents, such as can enumerate：The alcohols such as methanol, ethanol；The ethers such as tetrahydrofuran；Ethylene glycol list
The glycol ethers such as methyl ether, ethylene glycol monoethyl ether；The ethylene glycol alkyl ether second such as methylcellosolve acetate, ethyl cellosolve acetate
Esters of gallic acid；The diethylene glycol class such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether；Propylene glycol monomethyl ether, third
The propylene-glycol monoalky lether class such as glycol ether, propylene glycol propyl ether, propandiol butyl ether；Propylene glycol methyl ether acetate, propylene-glycol ethyl ether
The propylene glycol alkyl ether acetic acid esters such as acetic acid esters, propylene glycol propyl ether acetic acid esters, propandiol butyl ether acetic acid esters；Propylene glycol monomethyl ether propionic acid
The propylene glycol alkyl ether propionic acid ester such as ester, propylene-glycol ethyl ether propionic ester, propylene glycol propyl ether propionic ester, propandiol butyl ether propionic ester；
Toluene, dimethylbenzene etc. are aromatic hydrocarbon；The ketones such as MEK, 4- hydroxy-4-methyl-2-pentanones；With methyl acetate, acetic acid second
Ester, propyl acetate, butyl acetate, 2 hydroxy propanoic acid ethyl ester, 2- hydroxy-2-methyls methyl propionate, 2- hydroxy-2-methyl propionic acid second
Ester, hydroxy methyl acetate, hydroxyl ethyl acetate, Butyl Glycolate, methyl lactate, ethyl lactate, propyl lactate, lactic acid fourth
Ester, 3- hydroxy methyl propionates, 3- hydroxypropionates, 3- hydracrylic acids propyl ester, 3- hydroxy methyl propionates, 3- butoxy propionic acid second
The esters such as ester, 3- butoxy propyl propionate, 3- butoxy butyl propionates.
In these organic solvents, from dissolubility, with each composition reactivity and film formation easiness aspect,
Glycol ethers, glycol alkyl ether acetate esters, esters and diethylene glycol class can preferably be used.Form the tree of the base material of the present invention
In the resin combination of lipid layer 5, these organic solvents may be used singly or in combination of two or more.
When manufacture forms the resin combination of the resin bed 5 of the base material of the present invention, with above-mentioned dially phthalate tree
Fat is suitably added the polyfunctional monomer and Photoepolymerizationinitiater initiater of necessary amount, then added as needed thereto as main component
Plus stating additive, be mixed and stirred for.
[manufacture method of light sintering thermoplastic resin membrane's base material]
As the method for forming the resin bed 5 with cross-linked structure on the top layer of base material 1, it is wet that print process etc. can be enumerated
Method.As wet method, can use：Dip coating, flow coat method, rolling method, stick coating method, silk screen print method, curtain coating method, intaglio printing
Method known to method, flexographic printing process etc..
It is not particularly limited for the base material 1 used in the base material of the present invention, it is, for example, possible to use makrolon (PC),
Polyethylene terephthalate (PET), polyimides (PI), polyether sulfone (PES), PEN (PEN) etc.
Flexible plastic film and these films are imparted with gas barrier property, the laminated film of hard conating as synthetic resin base material.
In the case of the resin bed 5 that the base material of the present invention is formed by actinic energy ray curable resion composition, as
Radiation source, it can be adapted to use low pressure mercury lamp, medium pressure mercury lamp, high-pressure sodium lamp, ultrahigh pressure mercury lamp, xenon lamp or metal halide lamp
Deng.The resin of the film substrate 1 of the present invention is formed by the resin combination beyond actinic energy ray curable resion composition
In the case of layer 5, in addition, active energy beam can also be used as by the use of laser beam, electron beam etc..
[conducting channel substrate and its manufacture method]
Then, the conducting channel substrate and its manufacture method of the present invention are illustrated.The conducting channel substrate of the present invention
Formed with circuit pattern on the base material of the invention described above.
The formation of the circuit pattern of the conducting channel substrate of the present invention for example can be by being coated with, printing conductive composition
Formed etc. wet method.As wet method, such as can use：Ink-vapo(u)r recording, silk screen print method, spin-coating method, stick coating method, slit apply
Cloth method, dip coating, spraying process, woodburytype, flexographic plate print process, intaglio plate hectograph method, relief printing plate hectograph method, micro-contact printing
Method known to method, letterpress reverse printing method etc..
The present invention conducting channel substrate circuit pattern formation when, using print process in the case of, as electric conductivity group
Compound, for example, gold, silver, copper, nickel, zinc, aluminium, calcium, magnesium, iron, platinum, palladium, tin, chromium, lead etc. can be included in appropriate solvent
The alloys of these metals of metallic particles and silver/palladium etc., silver oxide, organic silver, organic gold etc. under relatively low temperature heat differentiation and
Obtain the oxidation of the conductive metals such as the pyrolytic metallic compound, zinc oxide (ZnO), tin indium oxide (ITO) of conductive metal
Composition granule can also include Polyglycolic acid fibre/polystyrolsulfon acid (PEDOT/PSS), polyaniline as conductive component
Deng electroconductive polymer.In addition, the species of the solvent of unlimited electrical conductivity composition, can suitably select to be suitable to conductive material
Dissolving or scattered solvent.Such as it can use：Water, hydrocarbon system, alcohol system, ketone system, ether system, ester system, fluorine system etc. it is various organic
Solvent.
In conductive composition, in addition to conductive material, can be added as needed on the Binder Compositions such as resin,
Antioxidant, the various catalyst for promoting epithelium formation, various surface tension modifiers, levelling agent, release promoter etc..
In these conductive compositions, dispersed nano-silver particles in solvent and are mixed with the releasing agents such as low molecule organosilicon, fluorine system table
The conductive composition of the surface tension modifiers such as face activating agent shows excellent figure particularly suitable for letterpress reverse printing method
Case performance and high electric conductivity is shown using low-temperature sintering, therefore can be adapted to use.
In the manufacture method of the conducting channel substrate of the present invention, the sintering of the circuit pattern formed on the base material of the present invention
Sintered using light.Light sinters the light irradiation for preferably having used flash lamp.Flash lamp is sealed with luminous in the pipe for quartz, glass etc.
The lamp of gas (Xe, Kr, Ar, Ne etc.), lighted, therefore can utilized with the μ s of μ s of the fluorescent lifetime 1~5000 extremely short time
The spectrum in the wide region of 200nm to 1100nm wavelength is irradiated.From the easiness aspect of purchase, Xe is preferably sealed with
Xenon flash lamp.
Embodiment
Hereinafter, the present invention is described in more detail using embodiment.But the present invention is not limited to these embodiments.
＜ embodiments 1 and reference example ＞
Each composition (unit is mass parts) is mixed using the formula shown in table 1 below, each composition is sufficiently stirred, makes its molten
Solution, is then filtered using 0.45 μm of molecular filter, prepares resin combination.Using bar coater, gained resin combination is applied
Be distributed in 125 μ m-thicks as base material PET film (Japan spin Co., Ltd. manufacture：Cosmo Shine A4300) on, at 90 DEG C
Lower heating 5 minutes, makes solvent volatilize.Afterwards, using high-pressure sodium lamp, accumulated light 2000mJ/cm is utilized2Active energy beam
Make resin composition, resin bed is formed on base material, make film substrate.The thickness of resin bed after solidification is 2~3 μ
m。
Use (the T355B of screen number 355：Emulsion is thick 5 μm) silk-screen plate, by silk-screen printing to made of above-mentioned steps
Base material assigns as the Ag pastes of conductive composition that (Argent grain, the silver that average grain diameter 20nm is dispersed with terpineol contain
The mass % of rate=40 Nano Silver paste), form the circuit pattern of 1.0 μm of thickness.The circuit pattern is utilized into xenon flash lamp (lamp
Power：Under 750V, the μ seconds of pulse length 2300,2600 μ seconds, air) light sintering is carried out, make conducting channel substrate.For gained
Conducting channel substrate, line resistance value is evaluated using Milliohm HiTester3540 (manufacture of Zhi Electric Co., Ltd), is used
Loresta GP (manufacture of Mitsubishi Chemical Analytech Co., Ltd.s) evaluate sheet resistance values, to according to line electricity
The resistivity value that resistance and line width, thickness, length of arrangement wire calculate is evaluated.Acquired results are remembered in table 1 in the lump.In addition,
The electron micrograph of a part for the circuit pattern of the conducting channel substrate of embodiment 1 is shown in Fig. 2, shows to join in Fig. 3
Examine the electron micrograph of a part for the circuit pattern of the conducting channel substrate of example.Based on these electron micrographs,
Evaluate the indentation of the base material of electrode both sides.〇 will be denoted as without indentation, shape also good situation, no indentation but electrode cracks
Situation be denoted as △, both sides occur indentation situation be denoted as ×.
＜ comparative examples ＞
Except not on base material set resin bed in addition to, with as described above the step of, make conducting channel substrate, utilize
Same method, line resistance value, sheet resistance values, resistivity value are evaluated.Acquired results are remembered in table 1 in the lump.In addition, figure
The electron micrograph of a part for the circuit pattern of the conducting channel substrate of comparative example is shown in 4.
[table 1]
※1：Do not turn on
※2：It can not be determined due to sintering deficiency
It can be seen from above-mentioned table 1, light sintering thermoplastic resin membrane base material of the invention sinters also not even if light is carried out
The circuit pattern for being formed at surface can be made to crack, break.In addition, in embodiment 1, the base material of electrode both sides has no indentation,
Shape is also good, and in reference example, the base material of electrode both sides has no indentation, but electrode slightly cracks.Understand the electrode of comparative example
Indentation occurs for the base material of both sides.(reference picture 2~4)
Description of reference numerals
1 base material
2 films
3 conductors
4 depressions
5 resin beds
Claims (4)
1. a kind of smooth sintering resin film base material, it is characterised in that the resin film base material includes base material and is formed at the base
Curable resin layer on material, it is more than 140 DEG C and 250 DEG C that the resin bed, which has cross-linked structure and glass transition temperature,
Hereinafter,
The resin bed includes any in diallyl phthalate resin and diallyl isophthalate resins
More than kind.
2. smooth sintering resin film base material according to claim 1, wherein, the resin bed is by irradiating active energy
Obtained from amount ray is solidified.
3. a kind of conducting channel substrate, it is characterised in that on the light sintering resin film base material described in claim 1 or 2
Formed with circuit pattern.
4. a kind of manufacture method of conducting channel substrate, it is characterised in that it is the conducting channel substrate described in claim 3
Manufacture method, circuit pattern is formed on the smooth sintering resin film base material, light sintering then is carried out to the circuit pattern.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013073467 | 2013-03-29 | ||
| JP2013-073467 | 2013-03-29 | ||
| PCT/JP2014/057359 WO2014156844A1 (en) | 2013-03-29 | 2014-03-18 | Thermoplastic resin film base for optical firing, conductive circuit board using same, and method for manufacturing said conductive circuit board |
Publications (2)
| Publication Number | Publication Date |
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| CN105073416A CN105073416A (en) | 2015-11-18 |
| CN105073416B true CN105073416B (en) | 2018-01-23 |
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| CN201480019404.3A Active CN105073416B (en) | 2013-03-29 | 2014-03-18 | Light sintering thermoplastic resin membrane base material, conducting channel substrate and its manufacture method using it |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP6441212B2 (en) |
| KR (1) | KR102292668B1 (en) |
| CN (1) | CN105073416B (en) |
| TW (1) | TWI636878B (en) |
| WO (1) | WO2014156844A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US10899940B2 (en) * | 2017-01-25 | 2021-01-26 | Xerox Corporation | Interlayer printing process |
| CN109986599B (en) * | 2017-12-29 | 2020-10-02 | 北京纳米能源与系统研究所 | Triboelectric intelligent skin, manipulator and robot |
| CN114746270A (en) * | 2019-12-24 | 2022-07-12 | Dic株式会社 | Laminate, printed wiring board, flexible printed wiring board, electromagnetic wave shield, and molded article |
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| CN101801674A (en) * | 2007-05-18 | 2010-08-11 | 应用纳米技术控股股份有限公司 | metallic ink |
| CN102112562A (en) * | 2008-05-15 | 2011-06-29 | 应用纳米技术控股股份有限公司 | Photo-curing process for metallic inks |
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| JPH03281622A (en) * | 1990-03-30 | 1991-12-12 | Hitachi Ltd | Photocurable diallyl phthalate resin composition and printed circuit board prepared by using the same |
| JPH0580521A (en) * | 1991-09-20 | 1993-04-02 | Hitachi Ltd | Photosetting resist composition and production of printed circuit board by using this composition and printed circuit board |
| JP2004223870A (en) | 2003-01-23 | 2004-08-12 | Nippon Zeon Co Ltd | Laminate and its use |
| US7439285B2 (en) * | 2004-01-23 | 2008-10-21 | Printar Ltd. | Liquid thermosetting ink |
| EP2913722A1 (en) | 2004-11-24 | 2015-09-02 | NovaCentrix Corp. | Electrical, plating and catalytic uses of metal nanomaterial compositions |
| JP2009124029A (en) * | 2007-11-16 | 2009-06-04 | Shinshu Univ | Method of manufacturing electronic circuit board using ink jetting |
| JP2009124032A (en) * | 2007-11-16 | 2009-06-04 | Shinshu Univ | Method of manufacturing printing type electronic circuit board |
| JP5505778B2 (en) * | 2009-12-24 | 2014-05-28 | 日本ゼオン株式会社 | Film for multilayer printed circuit boards |
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2014
- 2014-03-18 JP JP2015508372A patent/JP6441212B2/en active Active
- 2014-03-18 WO PCT/JP2014/057359 patent/WO2014156844A1/en active Application Filing
- 2014-03-18 CN CN201480019404.3A patent/CN105073416B/en active Active
- 2014-03-18 KR KR1020157031158A patent/KR102292668B1/en active IP Right Grant
- 2014-03-28 TW TW103111737A patent/TWI636878B/en active
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| CN101801674A (en) * | 2007-05-18 | 2010-08-11 | 应用纳米技术控股股份有限公司 | metallic ink |
| CN102112562A (en) * | 2008-05-15 | 2011-06-29 | 应用纳米技术控股股份有限公司 | Photo-curing process for metallic inks |
| CN102398438A (en) * | 2010-09-15 | 2012-04-04 | 中国科学院化学研究所 | Method for preparing primary circuit by jet-printing metal conductive printing ink by virtue of laser or microwave processing |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2014156844A1 (en) | 2014-10-02 |
| TW201446505A (en) | 2014-12-16 |
| KR20150136530A (en) | 2015-12-07 |
| CN105073416A (en) | 2015-11-18 |
| JPWO2014156844A1 (en) | 2017-02-16 |
| KR102292668B1 (en) | 2021-08-24 |
| TWI636878B (en) | 2018-10-01 |
| JP6441212B2 (en) | 2018-12-19 |
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