CN103069340B - Photoreactive resin composition - Google Patents

Photoreactive resin composition Download PDF

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Publication number
CN103069340B
CN103069340B CN201180041381.2A CN201180041381A CN103069340B CN 103069340 B CN103069340 B CN 103069340B CN 201180041381 A CN201180041381 A CN 201180041381A CN 103069340 B CN103069340 B CN 103069340B
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mole
oligomerization
resin composition
ester body
dipentaerythritol pentaacrylate
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CN103069340A (en
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久保田正博
砥绵修一
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Murata Manufacturing Co Ltd
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Murata Manufacturing Co Ltd
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    • 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
    • H05K3/287—Photosensitive compositions
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0047—Photosensitive materials characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/0325—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polysaccharides, e.g. cellulose
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • 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
    • H05K3/0073—Masks not provided for in groups H05K3/02 - H05K3/46, e.g. for photomechanical production of patterned surfaces
    • H05K3/0076—Masks not provided for in groups H05K3/02 - H05K3/46, e.g. for photomechanical production of patterned surfaces characterised by the composition of the mask
    • 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
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
    • H05K3/061—Etching masks
    • H05K3/064—Photoresists

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Ceramic Engineering (AREA)
  • Materials For Photolithography (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

To provide a photoreactive resin composition which gives a coating film having excellent developability and which is used in the production of a circuit board, a multilayered substrate, or the like when a desired conductor pattern is formed on a substrate surface or on each of the substrates for constituting the multilayered substrate or the like. [Solution] A photoreactive resin composition which comprises (A) an electroconductive powder, (B) an acrylic copolymer or a cellulosic resin each containing carboxy groups, (C) a mixture of dipentaerythritol pentaacrylate and hexaacrylate, and (D) a photopolymerization initiator. The photoreactive resin composition is characterized in that the mixture of dipentaerythritol pentaacrylate and hexaacrylate (C) has a penta form ratio, represented by (penta form)/[(penta form)+(hexa form)], of 25 mol% or more and an oligomer content, represented by oligomer/[(penta form)+(hexa form)+oligomer], of 33 mol% or less.

Description

Light reactive resin composition
Technical field
The present invention relates to such as when manufacturing circuit substrate or multilager base plate etc., substrate surface or form multilager base plate etc. each substrate on form required conductive pattern time the light reactive resin composition that uses.
Background technology
In recent years, multifunction and the high performance of electronic equipment are just constantly accelerated, and also require miniaturization for the electronic devices and components used in this electronic equipment.Therefore, about the Wiring pattern used in this electronic devices and components, also require the counter-measure developed for its densification and high speed.In order to realize the high speed of its densification and signal, need the miniaturization realizing Wiring pattern etc.
In order to form fine thick-film conductor body distribution or through hole on aforesaid substrate, effectively photoetching process, described photoetching process carries out after referring to and the minus light reactive resin composition containing photoreactivity organic principle and electroconductive powder etc. being coated substrate exposing, development treatment.
But, because electroconductive powder cannot make light completely through, light generation scattering, so light during exposure is difficult to arrive film bottom.Therefore, as acrylic monomers contained in light reactive resin composition, Dipentaerythritol Pentaacrylate/six acrylate mixture (with reference to patent documentation 1) preferably using number of functional groups many and highly sensitive.
Prior art document
Patent documentation
Patent documentation 1: Japanese Patent Laid-Open 2000-199954 publication
Summary of the invention
Invent technical matters to be solved
But, if use Dipentaerythritol Pentaacrylate/six acrylate mixture as acrylic monomers, then produce the developability variation of film, stably cannot form the problem of fine distribution.
Therefore, fundamental purpose of the present invention be to provide a kind of when manufacturing circuit substrate or multilager base plate etc., substrate surface or form multilager base plate etc. each substrate on form required conductive pattern time the light reactive resin composition of film developability excellence that uses.
The technical scheme that technical solution problem adopts
The feature of light reactive resin composition of the present invention is, contain: acrylic copolymer containing carboxyl of (A) electroconductive powder, (B) or celluosic resin, (C) Dipentaerythritol Pentaacrylate/six acrylate mixture, (D) Photoepolymerizationinitiater initiater, and Dipentaerythritol Pentaacrylate/six acrylate mixture is more than 25 % by mole with the five-ester body ratio that five-ester body/(five-ester body+six ester body) represents, is less than 33 % by mole with the oligomerization scale of construction that oligomerization body/(five-ester body+six ester body+oligomerization body) represents.
Invention effect
The present inventor finds, six ester bodies contained in Dipentaerythritol Pentaacrylate/six acrylate mixture and the deterioration of amount to the developability of film of oligomerization body impact.
Utilize light reactive resin composition of the present invention, by making, the five-ester body ratio of Dipentaerythritol Pentaacrylate/six acrylate mixture is more than 25 % by mole, the oligomerization scale of construction is less than 33 % by mole, even if the Wiring pattern be formed on substrate is fine, the light reactive resin composition of film developability excellence also can be obtained.
Above-mentioned purpose of the present invention, other object, feature and advantage is illustrated further by the explanation of following invention embodiment.
The mode carried out an invention
Below, the acrylic copolymer of each composition of the formation light reactive resin composition in one embodiment of the present invention i.e. (A) electroconductive powder, (B) containing carboxyl or celluosic resin, (C) Dipentaerythritol Pentaacrylate/six acrylate mixture and (D) Photoepolymerizationinitiater initiater are described respectively.
(A) electroconductive powder
In one embodiment of the present invention, as electroconductive powder, Cu, Ni, Ag, Au, Pt can be used and contain the alloy of wherein at least a kind.
The shape of electroconductive powder can adopt the various shapes such as spherical, sheet, needle-like, considers light characteristic, dispersiveness, preferably uses spherical electroconductive powder.Here, the mean grain size of electroconductive powder is better in the scope of 1 ~ 5 μm.When mean grain size is less than 1 μm, when adding isopyknic conductor powder in resin, the surface area of powder increases, and thus covers more light, the light transmittance to thickener inside is reduced.On the other hand, when being greater than 5 μm, surfaceness during applying conductive thickener increases, and pattern accuracy and dimensional accuracy reduce.
The ratio of components of the electroconductive powder in light reactive resin composition is better 30 ~ 50 volume % in the composition except organic solvent.When the ratio of components of electroconductive powder is less than 30 volume %, easily there is linewidth shrink and the broken string of conductive pattern, on the other hand, when more than 50 volume %, the transmission of light can be affected, be difficult to the enough photo-curables obtaining composition.
(B) acrylic copolymer containing carboxyl or celluosic resin
In one embodiment of the present invention, the acrylic copolymer containing carboxyl such as can manufacture by making unsaturated carboxylic acid and the copolymerization of alkene unsaturated compound.As unsaturated carboxylic acid, can exemplified by acrylic, methacrylic acid, maleic acid, fumaric acid, vinyl acetic acid and their acid anhydrides etc.On the other hand, as alkene unsaturated compound, can the acrylic acid acid esters such as exemplified by acrylic methyl esters, ethyl acrylate, the methacrylate such as methyl methacrylate, β-dimethyl-aminoethylmethacrylate, the fumarates etc. such as monomethyl ester.
As the celluosic resin containing carboxyl, the compound preferably having glycidyl and unsaturated double-bond containing the cellulose derivative or make of the carboxyl shown in following chemical formula 1 and/or the compound with isocyanate group and unsaturated double-bond add the compound being formed in carboxylic cellulose derivative.
In chemical formula 1, R 1represent the alkyl ,-CR of hydrogen atom, carbon number 1 ~ 4 2cOOH (R 2represent the alkyl of carbon number 2 ~ 4, phenyl or cyclohexyl) ,-C 3h 6oH or-COCH 3, each R 1can be the same or different, each glucose unit at least comprises-the CR of 0.1mol 2cOOH.
[changing 1]
In one embodiment of the present invention, the acrylic copolymer containing carboxyl or the ratio of components of celluosic resin are better containing 16 ~ 53 % by weight in the total amount of (B) ~ (D).When this ratio of components is less than 16 % by weight, the distribution of these resins in the film formed easily becomes uneven, is therefore difficult to obtain enough photo-curables and the photocuring degree of depth, so be difficult to form pattern by development.On the other hand, when being greater than 53 % by weight, pattern distortions when easily burning till and linewidth shrink.
(C) Dipentaerythritol Pentaacrylate/six acrylate mixture
Because electroconductive powder cannot make light completely through, light generation scattering, so light during exposure is difficult to arrive film bottom.Therefore, as the composition of light reactive resin, preferably use Dipentaerythritol Pentaacrylate/six acrylate mixture that functional group is many and highly sensitive.Dipentaerythritol Pentaacrylate/six acrylate mixture makes dipentaerythritol carry out esterification to manufacture by utilizing acrylic acid under the existence of acid catalyst and organic solvent.Esterification cannot 100% to be carried out.Some polymerization reaction take place in the manufacture of Dipentaerythritol Pentaacrylate/six acrylate mixture.Therefore, be in fact made up of Dipentaerythritol Pentaacrylate (five-ester body), dipentaerythritol acrylate (six ester bodies), oligomerization body three kinds.Wherein, six ester bodies and oligomerization body make the developability deterioration of film.Therefore, by five-ester body ratio is controlled more than 25 % by mole, the oligomerization scale of construction is controlled, below 33 % by mole, the deterioration of the developability of this film can be prevented.Here, five-ester body defines than by five-ester body/(five-ester body+six ester body), and the oligomerization scale of construction is defined by oligomerization body/(five-ester body+six ester body+oligomerization body).
The acid catalyst used during esterification can exemplify sulfuric acid, p-toluenesulfonic acid etc.The organic solvent used during esterification can exemplify the aromatic hydrocarbons such as such as toluene, benzene, dimethylbenzene, the aliphatic hydrocarbon such as hexane, heptane, the ketone etc. of methyl ethyl ketone etc.
In one embodiment of the present invention, the ratio of components of Dipentaerythritol Pentaacrylate/six acrylate mixture is better containing 30 ~ 70 % by weight in the total amount of (B) ~ (D).By adopting such ratio of components, the coating strength after photocuring is high, can obtain enough photocuring degree of depth, and film does not have viscous sense, can make it have good operability.
(D) Photoepolymerizationinitiater initiater
Photoepolymerizationinitiater initiater adds in order to initiated polymerization makes exposure portion solidify.As Photoepolymerizationinitiater initiater; can be used together 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholino propane-1-ketone (initiating agent a), 2; 4-diethyl sulfenyl thioxanthones (initiating agent b), ethyl ketone; 1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-base]-; 1-(o-acetyl oxime) (initiating agent c), two (2; 4,6-trimethylbenzoyl) phenyl phosphine oxide (initiating agent d) and 1-hydroxycyclohexylphenylketone (initiating agent e).
Particularly as the ethyl ketone of initiating agent c, 1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-base]-, the content of 1-(o-acetyl oxime) is better 10 ~ 60 % by weight in Photoepolymerizationinitiater initiater.By adopting such content, good dissolubility can be kept when increasing necessary exposure hardly.As initiating agent c, can use such as Ciba Specialty Chemicals (チ バ ス ペ シ ャ リ テ ィ ケ ミ カ Le ズ society) IRGACURE OXE02 processed,
In one embodiment of the present invention, the ratio of components of Photoepolymerizationinitiater initiater is better containing 12 ~ 22 % by weight in the total amount of (B) ~ (D).By adopting such content, the storage stability of excellent resin combination can be realized while realizing enough resolution.
(E) organic solvent
In addition, can as required containing as the 1,5-PD of organic solvent and dipropylene glycol monomethyl ether etc. in light reactive resin composition of the present invention.
(F) other organic principle
Thixotropic agent, spreading agent, gelation preventing agent and levelling agent can also be suitably used as required in light reactive resin composition of the present invention.Levelling agent uses special acrylic polymers.Levelling agent preferably uses ethylcarbitol acetate solution.When using in as the 1,5-PD of organic solvent and dipropylene glycol monomethyl ether, the SP value (solubleness) of this levelling agent is better 8.0 ~ 9.5.
The inorganic powder such as glass powder and ceramic powders can also be contained in light reactive resin composition of the present invention.By this, the adaptation with substrate can be improved.As glass powder, the known glass powders such as borosilicic acid salt glass can be used.As ceramic powders, can use with the known low-temperature sintered ceramics powder such as sintered glass ceramics class pottery, glass complex class pottery, non-glass class pottery that are representative such as aluminium oxide and zirconia.
Embodiment 1
Manufacture light reactive resin composition as described below, evaluates it.
1. the manufacture of light reactive resin composition
In the present embodiment, each material used in the manufacture of light reactive resin composition is as described below.
(A) electroconductive powder
Copper powders: oxygen content 1.2 % by weight, mean grain size 3 μm, spherical.
Ratio of components: 38 volume % (in the composition except organic solvent)
(B) acrylic copolymer containing carboxyl or celluosic resin
Polymkeric substance a: after making methacrylic acid/methyl methacrylate copolymer, the epoxycyclohexyl-methyl methacrylate that to make relative to methacrylic acid be 0.2 times of molar weight carries out addition reaction, the acrylic copolymer containing alkene unsaturated double-bond obtained thus.Weight-average molecular weight Mw=20000.Acid number=100mgKOH/g.
Polymkeric substance b: after making methacrylic acid/methyl methacrylate copolymer, the epoxy radicals ethylbenzene that to make relative to methacrylic acid be 0.2 times of molar weight carries out the acrylic copolymer that addition reaction obtains.Weight-average molecular weight Mw=24000.Acid number=90mgKOH/g.
(C) Dipentaerythritol Pentaacrylate/six acrylate mixture
Monomer 1: five-ester body than 55 % by mole, the oligomerization scale of construction 31 % by mole
Monomer 2: five-ester body than 45 % by mole, the oligomerization scale of construction 30 % by mole
Monomer 3: five-ester body than 35 % by mole, the oligomerization scale of construction 31 % by mole
Monomer 4: five-ester body than 30 % by mole, the oligomerization scale of construction 31 % by mole
Monomer 5: five-ester body than 25 % by mole, the oligomerization scale of construction 33 % by mole
Monomer 6: five-ester body than 25 % by mole, the oligomerization scale of construction 35 % by mole
Monomer 7: five-ester body than 20 % by mole, the oligomerization scale of construction 33 % by mole
Monomer 8: five-ester body than 30 % by mole, the oligomerization scale of construction 35 % by mole
Monomer 9: five-ester body than 35 % by mole, the oligomerization scale of construction 44 % by mole
Monomer 10: five-ester body than 20 % by mole, the oligomerization scale of construction 30 % by mole
Monomer 11: five-ester body than 10 % by mole, the oligomerization scale of construction 32 % by mole
Monomer 12: five-ester body than 20 % by mole, the oligomerization scale of construction 35 % by mole
Here, five-ester body defines than by five-ester body/(five-ester body+six ester body), and the oligomerization scale of construction is defined by oligomerization body/(five-ester body+six ester body+oligomerization body).
(D) Photoepolymerizationinitiater initiater
Initiating agent a:2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholino propane-1-ketone
Initiating agent b:2,4-diethyl sulfenyl thioxanthones
Initiating agent c: ethyl ketone, 1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-base]-, 1-(o-acetyl oxime)
Initiating agent d: two (2,4,6-trimethylbenzoyl) phenyl phosphine oxide
Initiating agent e:1-hydroxycyclohexylphenylketone
(E) organic solvent
Organic solvent a:1,5-pentanediol
Organic solvent b: dipropylene glycol monomethyl ether
(F) other organic principle
Thixotropic agent: polyamide-based (solid constituent 70%)
Spreading agent: high-molecular-weight poly carboxylic acid amides amine salt (solid constituent 75%)
Gelation preventing agent: benzotriazole
Levelling agent: special acrylic polymers (ethylcarbitol acetate solution, solid constituent 50%, SP value 8.81)
Weigh the above-mentioned each material except levelling agent according to the weight ratio shown in following table 1, table 2 and mix.Then, undertaken mixing by three-roll mill, then weigh levelling agent according to the weight ratio shown in table 1, table 2 and mix, making the sample 1 ~ 12 of light reactive resin composition.About the unit in each table, except five-ester body than and except the unit of the oligomerization scale of construction is % by mole, the unit of resolution is μm, unit is all % by weight.
2. the manufacture of ceramic green sheet
First, by the copolymerization ratios of borosilicic acid salt glass powder 37.3g, alumina powder 24.9g, methacrylic acid/methyl methacrylate with weight basis count 25/75 multipolymer (weight-average molecular weight Mw=50000) 6.2g, ethanol 3.1g and dipropylene glycol monomethyl ether 0.5g mix, make slurry.Then, the slurry made is configured as sheet by scraping the skill in using a kitchen knife in cookery, at 100 DEG C, drying 1 hour, makes the ceramic green sheet that sheet thickness is 30 μm.Although dipropylene glycol monomethyl ether can dissolve above-mentioned ceramic green sheet, become can not dissolve by Dipentaerythritol Pentaacrylate/six acrylate mixture of interpolation more than 0.5 times weight.
3. the mensuration of resolution
Each sample of photoelectric sensitivity conductive thickener is coated on the whole surface on the ceramic green sheet made as mentioned above by serigraphy after, at 60 DEG C, drying 15 minutes, forms the thickener film of thickness 10 ~ 12 μm.Then, across describing there is the photomask that lines (L) and interval (S) are the Wiring pattern of identical thickness, by ultra high pressure mercury light irradiation exposure 500mJ/cm with the thickness of 12 ~ 50 μm 2active ray, thus exposure-processed is carried out to thickener film.Then, use the aqueous sodium carbonate of 0.5%, carry out development treatment with the development time of 1.1 times of unexposed portion development time.
Then, observe Wiring pattern, judge the resolution of each sample according to the finest Wiring pattern of gained.That is, using the value of the thickness value of the finest Wiring pattern of fine Wiring pattern not in the Wiring pattern that interval (S) place is connected and lines (L) do not disconnect as expression resolution.
4. the manufacture of multilager base plate
Use the thickener of sample 1, across describing figuratum mask with the thickness of 13 μm, by ultra high pressure mercury light irradiation 500mJ/cm 2active ray, thus exposure-processed is carried out to thickener film.Then, use the aqueous sodium carbonate of 0.5%, carry out development treatment with the development time of 1.1 times of unexposed portion development time, thus make the ceramic green sheet that 5 pieces are formed with the pattern of L/S=13/13 (μm).Then, these ceramic green sheets are overlapping, under 200MPa, the condition of 60 DEG C, carry out the hot pressing of 1 minute.Then, after implementing ungrease treatment, at N at 900 DEG C 2in burn till, thus the multilayer aluminum oxide substrate that internal layer is formed with the pattern of L/S=10/10 (μm) can be formed in.
[table 1]
Sample 1 Sample 2 Sample 3 Sample 4 Sample 5 * sample 6
Copper powders 76.21 76.21 76.21 76.21 76.21 76.21
Polymkeric substance a 2.08 2.08 2.08 2.08 2.08 2.08
Polymkeric substance b 2.08 2.08 2.08 2.08 2.08 2.08
Monomer 1 4.19
Monomer 2 4.19
Monomer 3 4.19
Monomer 4 4.19
Monomer 5 4.19
Monomer 6 4.19
Initiating agent a 0.87 0.87 0.87 0.87 0.87 0.87
Initiating agent b 0.09 0.09 0.09 0.09 0.09 0.09
Initiating agent c 0.65 0.65 0.65 0.65 0.65 0.65
Initiating agent d 0.22 0.22 0.22 0.22 0.22 0.22
Initiating agent e 0.44 0.44 0.44 0.44 0.44 0.44
Organic solvent a 1.24 1.24 1.24 1.24 1.24 1.24
Organic solvent b 6.74 6.74 6.74 6.74 6.74 6.74
Thixotropic agent 0.22 0.22 0.22 0.22 0.22 0.22
Spreading agent 1.78 1.78 1.78 1.78 1.78 1.78
Gelation preventing agent 0.34 0.34 0.34 0.34 0.34 0.34
Levelling agent 2.85 2.85 2.85 2.85 2.85 2.85
Five-ester body 55 45 35 30 25 25
The oligomerization scale of construction 31 30 31 31 33 35
Resolution (μm) 13 14 14 14 14 25
* refer to outside the scope of protection of present invention
[table 2]
* sample 7 * sample 8 * sample 9 * sample 10 * sample 11 * sample 12
Copper powders 76.21 76.21 76.21 76.21 76.21 76.21
Polymkeric substance a 2.08 2.08 2.08 2.08 2.08 2.08
Polymkeric substance b 2.08 2.08 2.08 2.08 2.08 2.08
Monomer 7 4.19
Monomer 8 4.19
Monomer 9 4.19
Monomer 10 4.19
Monomer 11 4.19
Monomer 12 4.19
Initiating agent a 0.87 0.87 0.87 0.87 0.87 0.87
Initiating agent b 0.09 0.09 0.09 0.09 0.09 0.09
Initiating agent c 0.65 0.65 0.65 0.65 0.65 0.65
Initiating agent d 0.22 0.22 0.22 0.22 0.22 0.22
Initiating agent e 0.44 0.44 0.44 0.44 0.44 0.44
Organic solvent a 1.24 1.24 1.24 1.24 1.24 1.24
Organic solvent b 6.74 6.74 6.74 6.74 6.74 6.74
Thixotropic agent 0.22 0.22 0.22 0.22 0.22 0.22
Spreading agent 1.78 1.78 1.78 1.78 1.78 1.78
Gelation preventing agent 0.34 0.34 0.34 0.34 0.34 0.34
Levelling agent 2.85 2.85 2.85 2.85 2.85 2.85
Five-ester body ratio 20 30 35 20 10 20
The oligomerization scale of construction 33 35 44 30 32 35
Resolution (μm) 30 25 25 30 27 27
* refer to outside the scope of protection of present invention
From table 1, table 2, the five-ester body of Dipentaerythritol Pentaacrylate/six acrylate mixture is than being more than 25 % by mole and the oligomerization scale of construction is in the sample 1 ~ 5 of less than 33 % by mole, the deterioration of film developability is suppressed, therefore obtains the high resolving power of less than 15 μm.On the other hand, known sample 6 ~ 12, i.e. five-ester body, than being less than the sample of 25 % by mole or the oligomerization scale of construction more than in the sample of 33 % by mole, because film developability is deteriorated, can only obtain the resolution of about 25 ~ 30 μm.
Utilize light reactive resin composition of the present invention, by making, the five-ester body ratio of Dipentaerythritol Pentaacrylate/six acrylate mixture is more than 25 % by mole, the oligomerization scale of construction is less than 33 % by mole, can obtain the light reactive resin composition that film developability is excellent, can form fine Wiring pattern.
In addition, if use light reactive resin composition of the present invention, then fine Wiring pattern can be formed as mentioned above, therefore can be used for the conductive pattern forming multilager base plate manufacture, described multilager base plate is the sub-components and parts of high-frequency circuit electricity consumption such as chip coil, chip capacitor, chip LC wave filter, high-frequency model (such as VOC (voltage controlled oscillator)) or PLL (phaselocked loop (Japanese: position phase synchronous loop)) etc.) and so on high-frequency circuit board.
In circuit substrate in embodiments of the invention or the manufacture of multilager base plate, ceramic green sheet has been manufactured by using alumina powder, make aluminum oxide substrate, but be not limited to this, also can use and comprise with the ceramic green sheet of baryta, aluminium oxide and the monox pottery that is principal ingredient to manufacture substrate.The ceramic green sheet comprising glass ceramics can also be used to manufacture substrate.

Claims (1)

1. the light reactive resin composition used when forming required conductive pattern on substrate, is characterized in that, contain:
(A) electroconductive powder,
Acrylic copolymer (B) containing carboxyl or celluosic resin,
(C) Dipentaerythritol Pentaacrylate and dipentaerythritol acrylate potpourri,
(D) Photoepolymerizationinitiater initiater,
And the potpourri of Dipentaerythritol Pentaacrylate and dipentaerythritol acrylate is more than 25 % by mole with the five-ester body ratio that five-ester body/(five-ester body+six ester body) represents, it is less than 33 % by mole with the oligomerization scale of construction that oligomerization body/(five-ester body+six ester body+oligomerization body) represents
Wherein, the content of described (A) electroconductive powder is 30 ~ 50 volume %, described (B) acrylic copolymer containing carboxyl or celluosic resin in the total amount of (B) ~ (D) containing 16 ~ 53 % by weight, the potpourri of described (C) Dipentaerythritol Pentaacrylate and dipentaerythritol acrylate in the total amount of (B) ~ (D) containing 30 ~ 70 % by weight.
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JP6163876B2 (en) * 2013-05-24 2017-07-19 株式会社村田製作所 Photosensitive paste
JPWO2015040908A1 (en) * 2013-09-20 2017-03-02 東洋紡株式会社 Photosensitive conductive paste, conductive thin film, electric circuit, and touch panel
TW201539483A (en) * 2014-04-02 2015-10-16 Toyo Boseki Photosensitive conductive paste, conductive thin film, electrical circuit and touch panel
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