CN103176362A - Photosensitive resin composite for dry film photoresist - Google Patents

Photosensitive resin composite for dry film photoresist Download PDF

Info

Publication number
CN103176362A
CN103176362A CN2012105681560A CN201210568156A CN103176362A CN 103176362 A CN103176362 A CN 103176362A CN 2012105681560 A CN2012105681560 A CN 2012105681560A CN 201210568156 A CN201210568156 A CN 201210568156A CN 103176362 A CN103176362 A CN 103176362A
Authority
CN
China
Prior art keywords
resin composition
photosensitve resin
exposure
photosensitive resin
resin composite
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN2012105681560A
Other languages
Chinese (zh)
Inventor
石想勋
崔钟昱
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kolon Industries Inc
Kolon Corp
Original Assignee
Kolon Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kolon Corp filed Critical Kolon Corp
Publication of CN103176362A publication Critical patent/CN103176362A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • 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
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • 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
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
    • 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
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • 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
    • 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
    • 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
    • G03F7/037—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyamides or polyimides

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Materials For Photolithography (AREA)
  • Polymerisation Methods In General (AREA)
  • Graft Or Block Polymers (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
  • Manufacturing Of Printed Circuit Boards (AREA)

Abstract

The invention relates to a photosensitive resin composite contained in a dry film resist (photoresistance), and particularly relates to a photosensitive resin composite increases the resistance of developing liquid and improves the adherence of thin lines and the resolution ratio, and the stripping quality of a solid film formed through the photocuring of the photosensitive resin composite is excellent. Furthermore, when a laser direct exposure machine is used, the exposure can be realized by a few amount of exposure energy. For producers whose whole production speed is influenced by the speed of exposure technology or the works for forming images on PCBs, lead frames, PDPs or other displays, the photosensitive resin composite can greatly improve the production efficiency.

Description

The dry film photoresist Photosensitve resin composition
Technical field
The present invention relates to a kind of dry film photoresist Photosensitve resin composition.
Background technology
Photosensitve resin composition is to be used in printed circuit board (PCB) (Printed Circuit Board, PCB) or the forms such as the dry film photoresist of lead frame (Lead Frame) (Dry Film Photoresist, DFR) or aqueous photoresist printing ink (Liquid Photoresist Ink) use.
At present, not only in the manufacturing of printed circuit board (PCB) (PCB) or lead frame, also be widely used dry film photoresist in the manufacturings such as the ITO electrode of the spaced walls (Rib barrier) of plasma display panel (PDP) or other display, bus address (Bus Address) electrode, black matrix (Black Matrix).
When making PCB, lead frame etc., a most important operation is in discoid copper-clad laminate (Copper Clad Lamination Sheet is designated hereinafter simply as CCLS), the upper operation that forms circuit of Copper Foil (Copper Foil).The visualization way of using in this operation is called photoetching process (PhotoLithography), the master Using Image Plate that uses in order to carry out this photoetching process is called former figure (Artwork, make the normally used term in field at lead frame) or photomask (Photomask, the normally used term of field of semiconductor manufacture).
In addition, the image of described former figure is divided into the part of light transmission and the part of transmissive not, utilizes it to develop.This developing procedure is called exposure process.
Transmission by light and not transmission, the image of former figure turn and are mapped on CCLS or Copper Foil, and at this moment, the material that receives this light formation image is exactly photoresist (Photoresist is hereinafter referred to as PR).Thereby, PR be the image with former figure turn want lamination before penetrating or be coated to CCLS and Copper Foil on.
During exposure process, the manufacturer of PCB, lead frame uses the ultraviolet ray (Ultra Violet is hereinafter referred to as UV) that comprises the i line (365nm) of being launched by the superhigh temperature mercury vapor lamp that PR is exposed usually, thereby makes exposed portion generation polymerizing curable.Recently, utilize directly describing that laser carries out, namely do not need promoting rapidly without photomask exposure of former figure.Use the light of wavelength 350-410nm as the light source without photomask exposure, especially i line (365nm) or h line (405nm) more.But, compare with the superhigh temperature mercury vapor lamp exposure of usually implementing, without the time shutter of photomask exposure long, thereby need to use the PR of the high sensitivity of shortening time shutter.
Recently, need following Photosensitve resin composition, namely the sensitivity to superhigh temperature mercury vapor lamp or laser direct (LaserDirect) exposure is higher, patience to developer solution in developing procedure increases and can form highdensity circuit, and shortened the splitting time of cured film, can boost productivity with maximizing.
Summary of the invention
The object of the present invention is to provide a kind of dry film photoresist Photosensitve resin composition, possesses the patience to developer solution, thereby fine rule adherence and resolution have been improved, and, the peel property of the cured film that makes the Photosensitve resin composition photocuring and form is excellent, and, also can expose with a small amount of exposure energy when utilizing the direct exposure machine of laser.
According to one embodiment of the invention, provide a kind of and comprise the Photosensitve resin composition that has the photopolymerization compounds of ethylene unsaturated bond in [A] Photoepolymerizationinitiater initiater, [B] alkali development binder polymer and [C] molecule, should comprise N-phenylglycine by [A] Photoepolymerizationinitiater initiater, be somebody's turn to do the photopolymerization compounds that has ethylene unsaturated bond in [C] molecule and comprise the represented compound of following Chemical formula 1
＜Chemical formula 1 〉
Figure BDA00002636766000021
In formula, R 1Expression hydrogen atom or methyl, R 2Expression hydrogen atom or carbon number are the alkyl of 1-10, and m and n represent respectively the integer of 1-30 independently, and 2≤m+n≤30.
According to another embodiment of the present invention, provide a kind of and comprise the Photosensitve resin composition of [A] Photoepolymerizationinitiater initiater 0.5 to 20 % by weight, [B] alkali development binder polymer 30 to 70 % by weight and [C] photopolymerization compounds 10 to 60 % by weight.
Photosensitve resin composition is to use the direct special-purpose exposure machine of laser to expose according to another embodiment of the present invention, exposed portion generation photocuring, and form the photoresist pattern by developing procedure.
According to another embodiment of the present invention, provide a kind of Photosensitve resin composition that comprises the represented compound 1-20 % by weight of above-mentioned Chemical formula 1.
The invention effect
The present invention relates to be included in the Photosensitve resin composition in dry film photoresist, particularly, have the patience of developer solution and improved fine rule adherence and resolution, and the peel property of the cured film of Photosensitve resin composition being carried out photocuring and forming is excellent, and, can just can expose by enough a small amount of exposure energies when using the direct exposure machine of laser, for the manufacturer of the whole speed of production of rate of exposure technology or for generate the operation of image on PCB, lead frame, PDP and other display device, can greatly enhance productivity
Embodiment
According to one embodiment of the invention, provide a kind of and comprise the Photosensitve resin composition that has the photopolymerization compounds of ethylene unsaturated bond in [A] Photoepolymerizationinitiater initiater, [B] alkali development binder polymer and [C] molecule, should comprise N-phenylglycine by [A] Photoepolymerizationinitiater initiater, being somebody's turn to do the photopolymerization compounds that has ethylene unsaturated bond in [C] molecule comprises by the represented compound of following Chemical formula 1
＜Chemical formula 1 〉
Figure BDA00002636766000031
In formula, R 1Expression hydrogen atom or methyl, R 2Expression hydrogen atom or carbon number are the alkyl of 1-10, and m and n represent the integer of 1-30 independently of one another, and 2≤m+n≤30.
Dry film photoresist of the present invention has the patience of developer solution and has improved fine rule adherence and resolution with Photosensitve resin composition, and, the peel property of the cured film that makes the Photosensitve resin composition photocuring and form is excellent, and, just can expose with a small amount of exposure energy when using the direct exposure machine of laser.
In addition, according to Photosensitve resin composition of the present invention, preferably comprise N-phenylglycine.Thus, improve the sensitivity that Photosensitve resin composition directly exposes to laser, in the raising developing procedure to the patience of developer solution.
In addition, according to Photosensitve resin composition of the present invention, preferably, comprise the photopolymerization compounds that has ethylene unsaturated bond in [C] molecule and comprise the represented compound of above-mentioned Chemical formula 1.Thus, can further improve photosensitive resin to the direct sensitivity of exposure of laser, further improve in developing procedure the patience of developer solution, also shorten the splitting time of the cured film that makes the Photosensitve resin composition photocuring and form.
Photosensitve resin composition of the present invention reacts very sensitively to light, so also can occur to react fully to form circuit with exposure energy still less, have in [C] molecule in the photopolymerization compounds of ethylene unsaturated bond and comprise the represented compound of above-mentioned Chemical formula 1, thereby improved chemical resistance, can form high-resolution circuit in the process of each operation that forms the photoresist pattern, shortened the splitting time of the cured film that makes the Photosensitve resin composition photocuring and form, can boost productivity when forming image with maximizing.
Below further describe the present invention.
[A] Photoepolymerizationinitiater initiater
The Photoepolymerizationinitiater initiater that comprises in Photosensitve resin composition at dry film photoresist is to make the chain reaction of photo polymerization monomer begin the material that carries out by UV and other radiation, plays an important role in the curing of dry film photoresist.
Comprise N-phenylglycine in the present invention as Photoepolymerizationinitiater initiater.
N-phenylglycine reacts sensitively to the auroral poles end of 350-410nm, only also can cause sufficient light reaction with a small amount of luminous energy, thereby improves the sensitivity that laser is directly exposed, and raising is to the patience of developer solution and form good circuit in developing procedure.
The content that produces the N-phenylglycine of above-mentioned effect is the 0.05-2 % by weight of total composition, if content less than 0.05 % by weight, the reactivity of initiating agent die down and under a small amount of luminous energy (about 30mJ/cm 2Below) can't use; If surpass 2 % by weight, after exposure, the section of circuit can form serious inverted trapezoidal, therefore can't form required circuit width after etching work procedure in circuit, can cause (open) problem that opens circuit when serious.
Described Photoepolymerizationinitiater initiater can also further comprise normally used Photoepolymerizationinitiater initiater except N-phenylglycine.
described normally used Photoepolymerizationinitiater initiater can be two (the 2-chlorphenyls)-4 of 2,2'-, 4'-5,5'-four deximafens, 1-hydroxyl cyclohexyl benzophenone, 2,2-dimethoxy-1,2-hexichol second-1-ketone, 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholinyl third-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl) fourth-1-ketone, 2-hydroxy-2-methyl-1-phenyl third-1-ketone, 2,4,6-trimethylbenzene formyl diphenyl phosphine oxide, 1-4-(2-hydroxyl methoxyl) phenyl-2-hydroxy-2-methyl third-1-ketone, 2,4-diethyl thiazolone, 2-diuril oxazolone, 2,4-dimethylthiazole ketone, 3,3-dimethyl-4-methoxy benzophenone, benzophenone, 1-chloro-4-the third oxygen thiazolone, 1-(4-isopropyl phenyl) 2-hydroxy-2-methyl third-1-ketone, 1-(4-dodecylphenyl)-hydroxy-2-methyl third-1-ketone, 4-benzoyl-4 '-methyl dimethoxy thioether, the 4-dimethylaminobenzoic acid, 4-dimethylaminobenzoic acid methyl esters, the 4-dimethyl ethyl aminobenzoate, 4-dimethylaminobenzoic acid butyl ester, 4-dimethylaminobenzoic acid 2-Octyl Nitrite, 4-dimethylaminobenzoic acid 2-isopentyl ester, 2,2-diethoxy acetophenone, the benzyl ketone dimethylacetal, benzyl ketone 'beta '-methoxy diethyl acetal, 1-phenyl-1,2-propyl group dioxime-o, o'-(2-carbonyl) ethoxy ether, ortho-, meta-or p-benzoylbenzoic acid methyl esters, two (4-dimethylamino phenyl) ketone, 4,4 '-two (lignocaine) benzophenone, 4,4 '-dichloro benzophenone, benzyl, styrax, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, the styrax n-butyl ether, benzoin isobutyl ether, styrax uncle butyl ether, to the dimethylamino acetophenone, to tert-butyl group trichloroacetophenone, to tert-butyl group dichloroacetophenone, thioxanthones, 2-methyl thioxanthones, ITX, dibenzosuberenone, α-α-two chloro-is to metaphenoxy acetophenone, 4-dimethylaminobenzoic acid pentyl ester, the 9-phenylacridine, the n-phenylglycine, acridine compounds, the thioxanthones compounds, the anthracene compounds, coumarin kind compound, pyrazoline compounds, the dipolymer (dimer) of six aryl-imidazoles (hexaaryl-imidazole) etc., but be not limited thereto.
The content of described Photoepolymerizationinitiater initiater is to comprise 0.5 to 20 % by weight in Photosensitve resin composition.The content of described Photoepolymerizationinitiater initiater is in above-mentioned scope the time, can obtain sufficient sensitivity.
[B] alkali development binder polymer
Alkali development binder polymer of the present invention is the multipolymer of (methyl) acrylic acid and (methyl) acrylate.
Particularly, be the co-polypropylene acid macromolecule that selects the two or more monomers in the synthetic linear propylene's acid macromolecule of free methyl acrylate, methyl methacrylate, ethyl acrylate, methyl methacrylate, butyl acrylate, butyl methacrylate, acrylic acid, methacrylic acid, acrylic acid 2-hydroxyl ethyl ester, HEMA, acrylic acid 2-hydroxypropyl acrylate, methacrylic acid 2-hydroxypropyl acrylate, acrylamide, Methacrylamide, styrene and α-methyl styrene to obtain by copolymerization.
The preferred mean molecular weight of physical strength alkali development binder polymer of the present invention that consider the dry film photoresist coating, tracking property and circuit forms rear photoresist itself is 30,000 to 150,000g/mol, glass transition temperature are the macromolecular compound of 20 to 150 ℃, and the content in Photosensitve resin composition is 30 to 70 % by weight.
The content of described alkali development binder polymer is in above-mentioned scope the time, forms the effect that can obtain to improve the fine rule adhesion force after circuit.
The photopolymerization compounds that has ethylene unsaturated bond in [C] molecule
In order to have the patience of developer solution and to improve fine rule adhesion force and resolution, and shorten the splitting time of the cured film that the Photosensitve resin composition photocuring is formed, the photopolymerization compounds that has ethylene unsaturated bond in molecule of the present invention comprises the represented compound of following Chemical formula 1
＜Chemical formula 1 〉
Figure BDA00002636766000061
In formula, R 1Expression hydrogen atom or methyl, R 2Expression hydrogen atom or carbon number are the alkyl of 1-10, and m and n represent respectively the integer of 1-30 independently, and 2≤m+n≤30.
Change the R of the reactive unsaturated double-bond of display light section 1Structure, can replace hydrogen atom or methyl, if during hydrogen atom, photoreactivity increases, the fine rule adherence improves.
R 2And m and n be when satisfying above condition, has the patience of developer solution is improved fine rule adhesion force and resolution, and shorten the advantage of the splitting time of the cured film that the Photosensitve resin composition photocuring is formed.On the contrary, if comprise R 2Carbon number surpass 10 alkyl or the value of m+n surpasses 30, have the problem that development time increases.
In the present invention, the represented compound of above-mentioned Chemical formula 1 comprises 1 to 20 % by weight in Photosensitve resin composition, preferred 1.5 to 15 % by weight.The content of the compound that above-mentioned Chemical formula 1 represents is during less than 1 % by weight, and it has little effect; When surpassing 20 % by weight, can occur in the shortcoming that in the developing procedure after exposure, development time sharply rises.
Except the represented compound of Chemical formula 1, photopolymerization compounds of the present invention can also be included in the monomer that end has 2 vinyl at least.
the described monomer that has at least endways 2 vinyl can be ethylene glycol dimethacrylate, diethylene glycol dimethylacrylate (diethylene glycol dimethacrylate), TEG dimethylacrylate (tetraethylene glycol dimethacrylate), the propylene glycol dimethylacrylate, polypropylene glycol dimethacrylate (polypropylene glycol dimethacrylate), butanediol dimethylacrylate, neopentylglycol dimethacrylate, HDDMA, trimethylol-propane trimethacrylate (trimethyolpropanetrimethacrylate), the trihydroxy methyl propane triacrylate, the glycerine dimethylacrylate, dimethyl pentaerythritol acrylate, pentaerythrite trimethyl propylene acid alcohol, dipentaerythritol pentamethyl acrylate, two (the 4-methacryloxy diethoxy phenyl) propane (2,2-bis (4-methacryloxydiethoxyphenyl) propane) of 2,2-, two (the many ethoxyl phenenyls of the 4-methacryloxy) propane (2,2-bis (4-methacryloxypolyethoxyphenyl) propane) of 2,2-, 2-hydroxy-3-methyl acryloxy propyl methyl acid esters, the ethylene glycol diglycidylether dimethylacrylate, diethylene glycol diglycidyl ether dimethylacrylate, o-phthalic acid diglycidyl ester dimethylacrylate (phthalic acid diglycidyl ester dimethacrylate), glycerine polyglycidyl ether polymethacrylate (glycerin polyglycidyl etherpolymethacrylate), multifunctional (methyl) acrylate of amido-containing acid ester etc.
The content of described photopolymerization compounds preferably comprises 10 to 60 % by weight in Photosensitve resin composition.The content of described photopolymerization compounds is in above-mentioned scope the time, can obtain to have improved the effect of light sensitivity and resolution, adherence.
[D] other adjuvant
Photosensitve resin composition of the present invention can also comprise other adjuvant as required, and other adjuvant can use dibutyl phthalate, dibutyl phthalate (DHP), dioctyl phthalate, the diallyl phthalate as the phthalic ester form of plastifier; The triethylene glycol diacetate esters of glycol ester form, TEG diacetate esters; Para toluene sulfonamide, benzsulfamide, the n-butylbenzene sulfonamide of acid acid amides form; Triphenyl phosphate etc.
In the present invention, in order to improve the operability of Photosensitve resin composition, can also add leuco dye or coloring material.
Leuco dye can use three (4-dimethylamino-2-aminomethyl phenyl) methane, fluorane dyestuff.Wherein, when using leuco crystal violet, contrast more obviously, so can preferably use.When containing leuco dye, its content preferably comprises 0.1-10 quality % in Photosensitve resin composition.More than seeing preferred 0.1 % by weight from the viewpoint of contrast expression, see below preferred 10 % by weight from the viewpoint of storage stability.
Coloring material can be monohydrate, magenta, phthalocyanine green, auramine, paramagenta (Paramagenta), crystal violet, methyl orange, Nile blue 2B, Victoria blue, peacock green, diamond green, the alkali blue 20 of for example toluenesulfonic acid.When containing coloring material, preferably its addition is the 0.001-1 % by weight of Photosensitve resin composition.Being 0.001 % by weight when above at content, can improving operability, is 1 % by weight when following at content, has the effect of keeping storage stability.
As other adjuvant in addition, can also comprise thermal polymerization inhibitor, pigment, decolorant (discoloring agent), adhesion force promoter etc.
In the present invention, the Photosensitve resin composition of above-mentioned composition can be with dry film photoresist Photosensitve resin composition manufacturing, utilizes common painting method to carry out drying after applying the photosensitive resin layer of 10-400 μ m on the such common basement membrane of for example polyethylene terephthalate.Utilize the common diaphragms such as tygon to carry out lamination on the photosensitive resin layer of drying.In addition, dry film is exposed, develops carry out evaluation of physical property.The direct exposure machine of laser that comprises UV, visible rays laser etc. is preferably used in described exposure.
Below the preferred embodiments of the present invention and comparative example are elaborated.But these embodiment are a preferred embodiment of the present invention, and the present invention also can't help these embodiment and limits.
Embodiment 1,2 and comparative example 1,2
Dry film photoresist is estimated after making up and apply with the composition of Photosensitve resin composition according to the form below 1.At first, the Photoepolymerizationinitiater initiater class is dissolved in methyl ethyl ketone (MEK) as solvent and methyl alcohol (MeOH) afterwards, add photo polymerization monomer and alkali development binder polymer, utilize after machine mixer carries out the mixing of approximately 1 hour, utilize application bar (bar) to apply Photosensitve resin composition on the PET film of 30 μ m.Utilize heat generator to carry out drying to the photosensitive resin composition layer that applies, this moment, temperature and time was respectively 80 ℃, 5 minutes.Utilize diaphragm (PE) film that lamination is dried on photosensitive resin layer.
The reactivity of dry film is by utilizing lamination equipment (Hakuto Mach610i) with lamination roller pressure 4kgf/cm on CCL 2, after speed 2.0m/min carries out lamination, after the trapezoidal plate (Step Tablet) of Stuffer company system is set on the dry film surface, utilize INPREX IP-3600H to expose, at Na 2CO 3The aqueous solution of 1 % by weight, 30 ℃, expulsion pressure 1.5kgf/cm 2Condition under develop.
Utilize KOLON Test Artwork that the circuit physical property of dry film is estimated under given sensitivity, its result is shown in following table 2.
[table 1]
Figure BDA00002636766000091
The dry film photoresist that utilization is made in described embodiment and comparative example has been measured exposure, light sensitivity, fine rule adhesion force, resolution, degree of peeling off to copper coin, and with result shown in following table 2.
(1) exposure
Use exposure device INPREX IP-3600H to expose.
(2) light sensitivity
The sensitivity of using as reactive measuring is to measure take photoresist as benchmark with 21 sections trapezoidal plates of Stouffer Graphic Arts equipment company.
(3) fine rule adhesion force
After the PE film of the photosensitive dry film resist of removing manufacturing, utilize the heating crimping roller to carry out lamination on copper coin.At this, after utilizing the photomask of the wiring pattern with the 10-150 μ m that divides for unit by 5 μ m to carry out exposure imaging, measured the adhesion force of photoresist.
The wiring pattern of adhesion force is Line/Space=x:400 (unit: μ m), read the minimum value of the straight line the line that crawls in independent fine rule.
(4) resolution
Utilization has Line/Space=10:10-150:150 (unit: after the photomask of wiring pattern μ m) carries out exposure imaging, measured the resolution of photoresist.Resolution is in the photoresist pattern that forms in development after exposure, and unexposed portion is eliminated the minimum value of the pattern after clean.
(5) degree of peeling off
Degree of peeling off is measured by the following method.After the PE film of the photosensitive dry film resist of having removed manufacturing, utilize the heating crimping roller to carry out lamination on copper coin, Photosensitve resin composition is carried out exposure imaging, make the photocuring film of 50mmx50mm size.Then, use 3% sodium hydrate aqueous solution (temperature 50 C) to peel off.In the evaluation of degree of peeling off, with the photocuring film from time that copper coin is peeled off as splitting time.In addition, measured the size of peeling off test piece after peeling off.
S: little (less than 0.5cm)
M: in (0.5-2cm)
L: in (2-5cm)
[table 2]
Figure BDA00002636766000101
As shown in Table 2 above, compare with comparative example 1, the fine rule adhesion force of the dry film photoresist of the Photosensitve resin composition manufacturing that use the present invention relates to and resolution and light sensitivity are improved, and compare with comparative example 2, and degree of peeling off significantly reduces.
Those of ordinary skill in the art can easily carry out simple distortion of the present invention or change, and these distortion or change all belong to protection scope of the present invention.

Claims (4)

1. Photosensitve resin composition comprises:
[A] Photoepolymerizationinitiater initiater;
[B] alkali development binder polymer; And
The photopolymerization compounds that has ethylene unsaturated bond in [C] molecule,
Wherein, described [A] Photoepolymerizationinitiater initiater comprises N-phenylglycine, and the photopolymerization compounds that has ethylene unsaturated bond in described [C] molecule comprises the represented compound of following Chemical formula 1,
＜Chemical formula 1 〉
Figure FDA00002636765900011
In formula, R 1Expression hydrogen atom or methyl, R 2Expression hydrogen atom or carbon number are the alkyl of 1-10, and m and n represent respectively the integer of 1-30 independently, and 2≤m+n≤30.
2. Photosensitve resin composition according to claim 1, wherein, the content of described [A] Photoepolymerizationinitiater initiater is 0.5 to 20 % by weight; The content of described [B] alkali development binder polymer is 30 to 70 % by weight; And the content of described [C] photopolymerization compounds is 10 to 60 % by weight.
3. Photosensitve resin composition according to claim 1, wherein, described Photosensitve resin composition is to use the direct special-purpose exposure machine of laser to expose, exposed portion generation photocuring, and form the photoresist pattern by developing procedure.
4. Photosensitve resin composition according to claim 1, wherein, described Photosensitve resin composition comprises the compound that the Chemical formula 1 of 1-20 % by weight represents.
CN2012105681560A 2011-12-23 2012-12-24 Photosensitive resin composite for dry film photoresist Pending CN103176362A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR10-2011-0141392 2011-12-23
KR1020110141392A KR20130073509A (en) 2011-12-23 2011-12-23 Photosensitive resin composition for dry film photoresist

Publications (1)

Publication Number Publication Date
CN103176362A true CN103176362A (en) 2013-06-26

Family

ID=48636326

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2012105681560A Pending CN103176362A (en) 2011-12-23 2012-12-24 Photosensitive resin composite for dry film photoresist

Country Status (4)

Country Link
JP (1) JP2013134497A (en)
KR (1) KR20130073509A (en)
CN (1) CN103176362A (en)
TW (1) TW201327042A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105705998A (en) * 2013-08-07 2016-06-22 可隆工业株式会社 Photoresist resin composition for dry film photoresist
CN105900012A (en) * 2013-12-27 2016-08-24 可隆工业株式会社 Photosensitive resin composition for dry film photoresist
CN108255014A (en) * 2017-12-11 2018-07-06 珠海市能动科技光学产业有限公司 A kind of dry film photoresist containing modified polyurethane and photo-curing monomer

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015099480A1 (en) * 2013-12-27 2015-07-02 코오롱인더스트리 주식회사 Photosensitive resin composition for dry film photoresist
WO2016006264A1 (en) * 2014-07-10 2016-01-14 太陽インキ製造株式会社 Resin insulation layer formation method, resin insulation layer and printed circuit board

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004212805A (en) * 2003-01-07 2004-07-29 Asahi Kasei Electronics Co Ltd Photopolymerizable resin composition
CN1678957A (en) * 2002-09-03 2005-10-05 可隆株式会社 Photopolymerizable resin composition for sandblast resist
JP2007193322A (en) * 2005-12-22 2007-08-02 Asahi Kasei Electronics Co Ltd Positive photosensitive resin composition
CN101449208A (en) * 2006-08-03 2009-06-03 旭化成电子材料元件株式会社 Photosensitive resin composition and laminate

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4749305B2 (en) * 2005-10-05 2011-08-17 旭化成イーマテリアルズ株式会社 Photosensitive resin composition and laminate
JP2007101944A (en) * 2005-10-05 2007-04-19 Asahi Kasei Electronics Co Ltd Photosensitive resin composition and laminate

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1678957A (en) * 2002-09-03 2005-10-05 可隆株式会社 Photopolymerizable resin composition for sandblast resist
JP2004212805A (en) * 2003-01-07 2004-07-29 Asahi Kasei Electronics Co Ltd Photopolymerizable resin composition
JP2007193322A (en) * 2005-12-22 2007-08-02 Asahi Kasei Electronics Co Ltd Positive photosensitive resin composition
CN101449208A (en) * 2006-08-03 2009-06-03 旭化成电子材料元件株式会社 Photosensitive resin composition and laminate

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105705998A (en) * 2013-08-07 2016-06-22 可隆工业株式会社 Photoresist resin composition for dry film photoresist
CN105705998B (en) * 2013-08-07 2017-07-04 可隆工业株式会社 For the photosensitive resin composition of dry film photoresist
CN105900012A (en) * 2013-12-27 2016-08-24 可隆工业株式会社 Photosensitive resin composition for dry film photoresist
CN108255014A (en) * 2017-12-11 2018-07-06 珠海市能动科技光学产业有限公司 A kind of dry film photoresist containing modified polyurethane and photo-curing monomer

Also Published As

Publication number Publication date
JP2013134497A (en) 2013-07-08
TW201327042A (en) 2013-07-01
KR20130073509A (en) 2013-07-03

Similar Documents

Publication Publication Date Title
KR101141909B1 (en) Photosensit?e resin composition, photosensit?e element, method for resist pattern formation, and method for manufacturing printed wiring board
KR100932580B1 (en) The photosensitive resin composition, the photosensitive element, the formation method of a resist pattern, the manufacturing method of a printed wiring board, and the manufacturing method of the partition for plasma display panels using the same
TWI636329B (en) Photosensitive resin composition, photosensitive device, and forming method of resist pattern
KR101310407B1 (en) Photosensitive resin composition, photosensitive element, method for forming resist pattern, and method for manufacturing printed wiring board
CN103176362A (en) Photosensitive resin composite for dry film photoresist
KR101320225B1 (en) Photosensitive resin composition, photosensitive element, method of forming resist pattern, and process for producing printed wiring board
CN105182688A (en) Photosensitive Resin Composition, Photosensitive Element, Resist Pattern Manufacturing Method, And Printed Circuit Board Manufacturing Method
CN101981502A (en) Photosensitive resin composition, photosensitive element, method of forming resist pattern and method of producing printed wiring board
JP5151446B2 (en) Photosensitive resin composition, photosensitive element, resist pattern forming method and printed wiring board manufacturing method
KR101289569B1 (en) Photosensitive resin composition, photosensitive element, method for resist pattern formation, and method for manufacturing printed wiring board
KR20150063033A (en) Photosensitive resin composition, photosensitive element, method for forming resist pattern, and method for producing touch panel
JP2004301996A (en) Photosensitive resin composition
WO2013125429A1 (en) Photosensitive resin composition, photosensitive element, method for forming resist pattern, and method for manufacturing printed wiring board
WO2019173967A1 (en) Photosensitizer, photosensitive resin composition, photosensitive element, and method of producing wiring board
CN102854750B (en) Photosensitive resin composition, photosensitive element, method for forming resist pattern, method for producing lead frame, and method for producing printed wiring board
JPWO2007034610A1 (en) Photosensitive resin composition, photosensitive element, resist pattern forming method, printed wiring board manufacturing method, and plasma display partition forming method
KR101548412B1 (en) Photosensitive Resin Composition for Dry Film Photoresist
KR20140087164A (en) Photosensitive Resin Composition for Dry Film Photoresist
CN108027556B (en) Photosensitive resin composition, photosensitive element, method for forming resist pattern, and method for manufacturing touch panel
KR20150077031A (en) Photosensitive Resin Composition for Dry Film Photoresist
JP2015087427A (en) Photosensitive resin composition, photosensitive element, and method for forming resist pattern
KR20180077724A (en) Photosensitive resin composition for dry film photoresist
KR20120078499A (en) Photosensitive resin composition for dry film photoresist
WO2019173966A1 (en) Photosensitizer, photosensitive resin composition, photosensitive element, and method of producing wiring board
CN117693714A (en) Photosensitive composition, photosensitive element, and method for producing wiring board

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C02 Deemed withdrawal of patent application after publication (patent law 2001)
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20130626