CN105431778A - Photosensitive-resin composition - Google Patents

Photosensitive-resin composition Download PDF

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Publication number
CN105431778A
CN105431778A CN201480042096.6A CN201480042096A CN105431778A CN 105431778 A CN105431778 A CN 105431778A CN 201480042096 A CN201480042096 A CN 201480042096A CN 105431778 A CN105431778 A CN 105431778A
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CN
China
Prior art keywords
epoxy resin
photosensitive polymer
polymer combination
mass parts
phenyl
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
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CN201480042096.6A
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Chinese (zh)
Inventor
布施好章
吉野利纯
小岛正幸
大崎真也
佐藤邦明
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Showa Denko Materials Co ltd
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Hitachi Chemical Co Ltd
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Publication of CN105431778A publication Critical patent/CN105431778A/en
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    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • C08F290/144—Polymers containing more than one epoxy group per molecule
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
    • C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
    • C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
    • C08G59/1461—Unsaturated monoacids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C08L63/10—Epoxy resins modified by unsaturated compounds
    • 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
    • G03F7/0275—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with dithiol or polysulfide compounds
    • 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
    • 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
    • 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
    • H05K1/032—Organic insulating material consisting of one material
    • H05K1/0346—Organic insulating material consisting of one material containing N

Abstract

This invention pertains to a photosensitive-resin composition containing the following: (A) an acid-modified-vinyl-group-containing epoxy resin; (B) an acyl-phosphine-oxide photopolymerization initiator; (C) one or more additives selected from among (C1) alkylamino-benzene derivatives, (C2) pyrazoline sensitizers or anthracene sensitizers, (C3) one or more photopolymerization initiators selected from among imidazole photopolymerization initiators, acridine photopolymerization initiators, and titanocene photopolymerization initiators, (C4) one or more antioxidants selected from among hindered-phenol antioxidants, quinone antioxidants, amine antioxidants, sulfur antioxidants, and phosphorus antioxidants, and (C5) thiol-group-containing compounds; and (D) a photopolymerizable compound.

Description

Photosensitive polymer combination
Technical field
The present invention relates to photosensitive polymer combination, use the photosensitive element of this photosensitive polymer combination, permanent mask resist and possess the printing distributing board of this permanent mask resist.
Background technology
In the manufacture field of printing distributing board, carry out the operation forming permanent mask resist on printing distributing board.When using printing distributing board, permanent mask resist has the effect of the electrical insulating property preventing conductor layer from corroding or between maintenance conductor layer.In recent years, semiconductor element is undertaken by solder in the operation of flip-chip installation, wire-bonded installation etc. by printing distributing board, permanent mask resist also has the effect as soldering-resistance layer, namely prevents solder attachment in the unnecessary part of the conductor layer of printing distributing board.
In the past, the permanent mask resist in printing distributing board manufacture used compositions of thermosetting resin to be made by serigraphy, or use sense photosensitive resin composition is made by photographic process.Such as, at use FC (FlipChip, flip-chip), TAB (TapeAutomatedBonding, winding engages automatically) and COF (ChipOnFilm, membrane of flip chip) etc. mounting means flexible wiring sheet in, except IC chip, electronic unit, LCD (LiquidCrystalDisplay) panel and connection wiring pattern part, serigraphy thermoset resin is stuck with paste, carry out heat curing and form permanent mask resist (such as, patent documentation 1).
In addition, for the BGA (BallGridArray being equipped on electronic unit, ball grid array), CSP (ChipSizePackage, chip size packages) etc. conductor package substrate, (1) in order to carry out flip-chip installation by solder to semiconductor element on conductor package substrate, (2) in order to carry out wire-bonded to semiconductor element and conductor package substrate, or (3) are in order to be welded on conductor package substrate on parent substrate, need the permanent mask resist removing its bonding part.Therefore, when forming this permanent mask resist, use photographic process, that is: after photosensitive polymer combination being coated with drying, optionally irradiation ultraviolet radiation isoreactivity light makes it solidify, and uses developer solution only to remove non-irradiation unit and divides, form image.Photographic process is well considered to be applicable to a large amount of production from its workability, is therefore widely used in image formation (such as, patent documentation 2 ~ 4) of photosensitive polymer combination in electronic material industry.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2003-198105 publication
Patent documentation 2: Japanese Unexamined Patent Publication 11-240930 publication
Patent documentation 3: Japanese Unexamined Patent Publication 2010-235739 publication
Patent documentation 4: Japanese Unexamined Patent Publication 2011-133851 publication
Summary of the invention
The problem that invention will solve
But, when use described in patent documentation 2 ~ 4 with the addition of the photosensitive polymer combination of pigment, filler etc., pigment, filler etc. can hinder ultraviolet through or absorb ultraviolet, if therefore want the permanent mask resist of the such thick film of formation more than 20 ~ 40 μm, then sometimes fully cannot obtain the photocuring of the photosensitive polymer combination of bottom, consequently, the situation producing the undercutting that bottom is cut off after development is deposited.
If make the exposure of Ultraviolet radiation increase in order to the photo-curable improving bottom, then optical diffraction and halation become large, the live width in the pars intermedia (central part) of patterned section and most deep (bottom) is greater than the live width on surface element (top), therefore there is the deterioration producing resist shape or resolution reduces such problem.In addition, to cause because of oxygen inhibition on resist depth direction photocuring from the region about surface to 3 μm not enough, make resist upper break, thus also there is resist shape and worsen such problem.Therefore present situation is, when the permanent mask resist of the such thick film of formation more than 20 ~ 40 μm, and the good and photosensitive polymer combination of excellent in resolution of the photo-curable that there is not bottom.
Further, in recent years, with the miniaturization of electronic equipment, high performance, between the pore size of permanent mask resist and hole, the tendency that spacing has miniaturization is separated.Such as, pore size is used to be 100 μm and the spacing that separates between hole is that 100 μm or pore size are 80 μm and are spaced apart 80 μm of such fine patterns between hole.Therefore, such as, when flip-chip is installed, require while resolution improves, from the permanent mask resist of the excellent in stability of the viewpoint resist shape of fill solder.
The present invention completes in view of such problem, its objective is and photosensitive polymer combination is provided, use the photosensitive element of this photosensitive polymer combination, permanent mask resist and the printing distributing board possessing this permanent mask resist, described photosensitive polymer combination is due to the curability excellence bottom the peristome of hole, therefore the undercutting be cut off bottom can not producing and the disappearance on resist top, in addition due to the exposure of Ultraviolet radiation can not be made to increase, therefore the pars intermedia (central part) of patterned section and the live width in most deep (bottom) are not more than the live width of surface element, the rectilinearity that namely can form pattern contour is good and resist shape is excellent, the pattern of excellent in resolution.
In addition, the photosensitive polymer combination of the application of the invention is provided, can be formed with the miniaturization of electronic equipment in recent years and the photosensitive element separating the pattern of the formation excellent in stability of spacing between the pore size through miniaturization of high performance and hole, permanent mask resist and the printing distributing board possessing this permanent mask resist.
The method of dealing with problems
The present inventor etc. conduct in-depth research repeatedly in order to solve the problem, and found that can be solved by following invention.Namely the invention provides following photosensitive polymer combination, photosensitive element, permanent mask resist and printing distributing board.
[1] a kind of photosensitive polymer combination, sour modification that it comprises (A), containing vinyl epoxy resin, (B) acylphosphine oxide system Photoepolymerizationinitiater initiater, (C) adjuvant and (D) photopolymerizable compound, should (C) adjuvant be selected from least one in following material: (C1) alkyl amino benzene derivative; (C2) pyrazoline system sensitizer or anthracene system sensitizer; (C3) at least one Photoepolymerizationinitiater initiater in imidazoles system Photoepolymerizationinitiater initiater, acridine system Photoepolymerizationinitiater initiater and two luxuriant titanium system Photoepolymerizationinitiater initiaters is selected from; (C4) at least one antioxidant in hindered phenol system antioxidant, quinone system antioxidant, amine system antioxidant, sulphur system antioxidant and phosphorous antioxidant is selected from; And (C5) sulfur-bearing alcohol-based compounds.
[2] photosensitive element, its photographic layer that there is supporter and use the photosensitive polymer combination described in above-mentioned [1] to be formed on this supporter.
[3] a kind of permanent mask resist, is formed by the photosensitive polymer combination described in above-mentioned [1].
[4] printing distributing board, possesses the permanent mask resist described in above-mentioned [3].
The effect of invention
According to the present invention, the disappearance that do not produce the undercutting that is cut off of bottom and resist top can be obtained and can form that the rectilinearity of pattern contour is good and resist shape is excellent, the photosensitive polymer combination of the pattern of excellent in resolution, can be formed through the photosensitive element separating the pattern of the formation excellent in stability of spacing between the pore size and hole of miniaturization, forever mask resist and the printing distributing board possessing it.
Accompanying drawing explanation
Fig. 1 is the schematic cross-section of the resist using photosensitive polymer combination of the present invention to be formed.
Fig. 2 is the figure of the pattern form representing the negative mask that embodiment uses.
Fig. 3 is the figure of the pattern form representing the negative mask that embodiment uses.
Embodiment
[photosensitive polymer combination]
Embodiments of the present invention are (following, also be only called " present embodiment ") involved by photosensitive polymer combination (following containing vinyl epoxy resin for comprising (A) sour modification, also referred to as " (A) composition "), (B) acylphosphine oxide system Photoepolymerizationinitiater initiater is (following, also referred to as " (B) composition "), (C) adjuvant is (following, also referred to as " (C) composition ") and (D) light repeatability compound is (below, also referred to as " (D) composition ") photosensitive polymer combination, should (C) adjuvant be selected from least one in following material: (C1) alkyl amino benzene derivative is (following, also referred to as " (C1) composition "), (C2) pyrazoline system sensitizer or anthracene system sensitizer are (below, also referred to as " (C2) composition "), (C3) imidazoles system Photoepolymerizationinitiater initiater is selected from, at least one Photoepolymerizationinitiater initiater in acridine system Photoepolymerizationinitiater initiater and two luxuriant titanium system Photoepolymerizationinitiater initiaters is (following, also referred to as " (C3) composition "), (C4) hindered phenol system antioxidant is selected from, quinone system antioxidant, amine system antioxidant, at least one antioxidant in sulphur system antioxidant and phosphorous antioxidant is (following, also referred to as " (C4) composition "), and (C5) sulfur-bearing alcohol-based compounds is (following, also referred to as " (C5) composition ").
Below, each composition is described.
< (A) sour modification is containing vinyl epoxy resin >
The photosensitive polymer combination of present embodiment contains sour modification containing vinyl epoxy resin as (A) composition.
(A) as long as sour modification utilizes the organic acid containing vinyl to be just not particularly limited by the material of epoxy resin modification gained containing vinyl epoxy resin, preferably make epoxy resin (a) and react containing vinyl monocarboxylic acid (b) and the epoxy resin (a ') that obtains, be more preferably and make this epoxy resin (a ') react with the multi-anhydride (c) containing saturated base or unsaturated group further and the epoxy resin (a ") that obtains.
As epoxy resin (a), be preferably selected from least one in the epoxy resin of the structural unit had represented by following general formula (I) ~ (V).The epoxy resin of the structural unit had represented by each general formula is described.
(there is the phenolic resin varnish type epoxy resin of the structural unit represented by general formula (I))
First, as epoxy resin (a), preferably enumerate the phenolic resin varnish type epoxy resin of the structural unit had represented by following general formula (I), as the epoxy resin with such structural unit, preferably enumerate the phenolic resin varnish type epoxy resin represented by such as following general formula (I ')
[changing 1]
In general formula (I), R 11represent hydrogen atom or methyl, Y 1represent glycidyl.
In the phenolic resin varnish type epoxy resin with the structural unit represented by general formula (I), the content of the structural unit represented by general formula (I) is preferably greater than or equal to 70 quality %, more preferably greater than or equal 90 quality %, further preferably greater than or equal to 95 quality %.
In addition, general formula (I ') in, R 11 'represent hydrogen atom or methyl, Y 1 'represent hydrogen atom or glycidyl, and the mol ratio of hydrogen atom and glycidyl is preferably 0:100 ~ 30:70, is more preferably 0:100 ~ 10:90, more preferably 0:100.From the mol ratio of hydrogen atom and glycidyl, at least one Y 1 'represent glycidyl.General formula (I ') in, n1 represents the integer being more than or equal to 1.In addition, multiple R 11 'can be the same or different each other, multiple Y 1 'can be the same or different.
The integer of n1 as mentioned above for being more than or equal to 1, is preferably 10 ~ 200, is more preferably 30 ~ 150, more preferably 30 ~ 100.If n1 is in above-mentioned scope, then the tendency of the corrosion-resisting pattern having the balance that can obtain resist shape, resolution, thermotolerance, adaptation and electrical insulating property more excellent.
As the phenolic resin varnish type epoxy resin represented by general formula (I '), preferably enumerate such as phenol novolak type epoxy resin, cresol novolak type epoxy resin etc.These phenolic resin varnish type epoxy resins such as can obtain by utilizing known method to make the epihalohydrins such as the phenolics such as phenol resol resins, cresol novolac resin and chloropropylene oxide react.
As the phenolic resin varnish type epoxy resin represented by general formula (I '), business can buy such as YDCN-701, YDCN-702, YDCN-703, YDCN-704, YDCN-704L, YDPN-638, YDPN-602 is (above for aurification (strain) system is lived by Nippon Steel, trade name), DEN-431, DEN-439 (is DOW Chemical (strain) system above, trade name), EOCN-120, EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1012, EOCN-1025, EOCN-1027, BREN (is Japanese chemical drug (strain) system above, trade name), EPN-1138, EPN-1235, EPN-1299 (is BASF Japan (strain) system above, trade name), N-730, N-770, N-865, N-665, N-673, VH-4150, VH-4240 (is DIC (strain) system above, trade name) etc.
(there is the epoxy resin of the structural unit represented by general formula (II))
As epoxy resin (a), preferably enumerate the epoxy resin of the structural unit had represented by following general formula (II), as the epoxy resin with such structural unit, preferably enumerate the bisphenol A type epoxy resin represented by such as following general formula (II ') and bisphenol f type epoxy resin.
[changing 2]
In general formula (II), R 12represent hydrogen atom or methyl, Y 2represent glycidyl.
In the epoxy resin with the structural unit represented by general formula (II), the content of the structural unit represented by general formula (II) is preferably greater than or equal to 70 quality %, more preferably greater than or equal 90 quality %, further preferably greater than or equal to 95 quality %.
In addition, general formula (II ') in, R 12 'represent hydrogen atom or methyl, Y 2 'represent hydrogen atom or glycidyl, and the mol ratio of hydrogen atom and glycidyl is preferably 0:100 ~ 30:70, is more preferably 0:100 ~ 10:90, more preferably 0:100.From the mol ratio of hydrogen atom and glycidyl, at least one Y 2 'represent glycidyl.General formula (II ') in, n2 represents the integer being more than or equal to 1.In addition, multiple R 12 'can be the same or different, when n2 is more than or equal to 2, multiple Y 2 'can be the same or different.
The integer of n2 as mentioned above for being more than or equal to 1, is preferably 10 ~ 100, is more preferably 10 ~ 80, more preferably 15 ~ 60.If n2 is in above-mentioned scope, then the tendency of the corrosion-resisting pattern having the balance that can obtain resist shape, resolution, adaptation, thermotolerance and electrical insulating property more excellent.
Represented and Y by general formula (II ') 2 'for the bisphenol A type epoxy resin of glycidyl or bisphenol f type epoxy resin can obtain by such as making the epihalohydrins such as the hydroxyl of the bisphenol A type epoxy resin represented by following general formula (VII) or bisphenol f type epoxy resin and chloropropylene oxide react.
[changing 3]
In general formula (VII), R 12same as described above with n2.
If consider to obtain the corrosion-resisting pattern that the balance of resist shape, resolution, film strength, thermotolerance, insulating reliability, resistance to sudden heating and resolution is more excellent, then the use amount of epihalohydrins is preferably set to 2 ~ 10 moles relative to the hydroxyl 1 mole in the epoxy resin represented by general formula (VII).
From the viewpoint of same with it, when the epoxy resin represented by general formula (VII) and epihalohydrins react, preferably use base catalyst.As base catalyst, preferably enumerate such as alkaline earth metal hydroxide, alkali carbonate, alkali metal hydroxide etc., from the viewpoint of catalyst activity, the more preferably alkali metal hydroxide such as NaOH, potassium hydroxide, calcium hydroxide.In addition, its use amount is preferably 0.9 ~ 2 mole relative to the hydroxyl 1 mole in the epoxy resin represented by general formula (VII).
In the reaction of the epoxy resin represented by general formula (VII) and epihalohydrins, from the viewpoint of more improving reaction velocity, as organic solvent, preferably use the such as alcohols such as methyl alcohol, ethanol; The cellosolve such as methyl cellosolve, ethyl cellosolve class; The ethers such as tetrahydrofuran, diox; Dimethyl formamide, dimethyl acetamide, dimethyl sulfoxide (DMSO) polar organic solvent etc.Can be used alone a kind in these materials or combinationally use two or more, from the viewpoint of polarity adjustment, preferred compositions uses two or more.
In addition, temperature of reaction is preferably 20 ~ 120 DEG C, is more preferably 50 ~ 120 DEG C, and the reaction time is preferably 0.5 ~ 10 hour.If temperature of reaction and reaction time are in above-mentioned scope, then react not easily slack-off, not easily produce side reaction product in addition.
After above-mentioned reaction, preferably under heating decompression, by distillation by the distillation such as unreacted epihalohydrins, organic solvent removing, thus obtain the epoxy resin represented by general formula (II ').
In addition, from the viewpoint of obtaining the higher epoxy resin of purity, the epoxy resin obtained can be made again to be dissolved in organic solvent, and add the base catalysts such as above-mentioned alkali metal hydroxide and react.At this moment, from the viewpoint of raising reaction velocity, preferably with the phase transfer catalyst such as scope use quaternary ammonium salt, crown ether etc. relative to epoxy resin being 0.1 ~ 3 quality %.In this case, reaction is terminated the salt of rear generation etc. and passes through the removings such as filtration, washing, under heating decompression, organic solvent etc. is distilled removing further, thus highly purified epoxy resin can be obtained.
As the bisphenol A type epoxy resin represented by general formula (II ') or bisphenol f type epoxy resin, can business buy such as EPIKOTE807,815,825,827,828,834,1001,1004,1007 and 1009 (they being Mitsubishi Chemical's (strain) system, trade name above), DER-330, DER-301, DER-361 (being DOW Chemical (strain) system, trade name above), YD-8125, YDF-170, YDF-175S, YDF-2001, YDF-2004, YDF-8170 (above for Nippon Steel live that aurification (strain) is made, trade name) etc.
(there is the epoxy resin of the structural unit represented by general formula (III))
As epoxy resin (a), preferably enumerate the epoxy resin of the structural unit had represented by following general formula (III), as the epoxy resin with such structural unit, preferably enumerate the tris-phenol type epoxy resin represented by such as following general formula (III ').
[changing 4]
In general formula (III) and (III '), Y 3represent hydrogen atom or glycidyl, and the mol ratio of hydrogen atom and glycidyl is preferably 0:100 ~ 30:70.From the mol ratio of hydrogen atom and glycidyl, at least one Y 3represent glycidyl.Formula (III ') in, n3 represents the integer being more than or equal to 1.In addition, multiple Y 3can be the same or different.
The integer of n3 as mentioned above for being more than or equal to 1, is preferably 10 ~ 100, is more preferably 15 ~ 80, more preferably 15 ~ 70.If n3 is in above-mentioned scope, then can obtain the corrosion-resisting pattern that the balance of resist shape, resolution, thermotolerance, adaptation and electrical insulating property is more excellent.
In the epoxy resin with the structural unit represented by general formula (III), the content of the structural unit represented by general formula (III) is preferably greater than or equal to 70 quality %, more preferably greater than or equal 90 quality %, further preferably greater than or equal to 95 quality %.
As the tris-phenol type epoxy resin represented by general formula (III '), business such as FAE-2500, EPPN-501H, EPPN-502H (above is Japanese chemical drug (strain) system, trade name) etc. can be buied.
(there is the bis-phenol phenolic resin varnish type epoxy resin of the structural unit represented by general formula (IV))
As epoxy resin (a), preferably enumerate the bis-phenol phenolic resin varnish type epoxy resin of the structural unit had represented by following general formula (IV).
[changing 5]
In general formula (IV), R 13represent hydrogen atom, alkyl, aryl, aralkyl, sulfonic group or trihalomethyl, Y 4represent hydrogen atom or glycidyl.At least one Y 4represent glycidyl, multiple R 13can be the same or different.
R 13the carbon number of alkyl be preferably 1 ~ 20, be more preferably 1 ~ 12, more preferably 1 ~ 3.In addition, alkyl can be straight-chain also can be branched, can also by replacements such as halogen atom, alkyl, aryl, aralkyl, amino, amide group, alkoxys.
As alkyl, preferably enumerate such as methyl, ethyl, propyl group, isopropyl, butyl, isobutyl, sec-butyl, the tert-butyl group, amyl group, sec-amyl, isopentyl, neopentyl etc., in these, more preferably methyl.
As aryl, phenyl, xenyl, naphthyl, anthryl, phenanthryl etc. can be enumerated, be preferably the aryl of ring carbons number 6 ~ 20, be more preferably the aryl of ring carbons number 6 ~ 14.In addition, aryl also can by replacements such as halogen atom, alkyl, aryl, aralkyl, amino, amide group, alkoxys.
As aralkyl, as long as abovementioned alkyl hydrogen atom is just not particularly limited by the group that above-mentioned aryl replaces gained, such as benzyl, phenylethyl, phenyl propyl, naphthyl methyl etc. can be enumerated.In addition, aralkyl also can by replacements such as halogen atom, alkyl, aryl, aralkyl, amino, amide group, alkoxys.
In the epoxy resin with the structural unit represented by general formula (IV), the content of the structural unit represented by general formula (IV) is preferably greater than or equal to 70 quality %, more preferably greater than or equal 90 quality %, further preferably greater than or equal to 95 quality %.
If be in above-mentioned scope, then can obtain the corrosion-resisting pattern that the balance of resist shape, resolution, thermotolerance, adaptation and electrical insulating property is more excellent.
(there is the bis-phenol phenolic resin varnish type epoxy resin of the structural unit represented by general formula (V))
As epoxy resin (a), preferably enumerate the bis-phenol phenolic resin varnish type epoxy resin of the structural unit had represented by following general formula (V).
[changing 6]
In general formula (V), R 14represent hydrogen atom, alkyl, aryl, aralkyl, sulfonic group or trihalomethyl, Y 5represent hydrogen atom or glycidyl.At least one Y 5represent glycidyl, multiple R 14can be the same or different.In addition, as R 14alkyl, aryl, aralkyl, can illustrate and R 13the group that described group is identical, preferred form too.
In the epoxy resin with the structural unit represented by general formula (V), the content of the structural unit represented by general formula (V) is preferably greater than or equal to 70 quality %, more preferably greater than or equal 90 quality %, further preferably greater than or equal to 95 quality %.If be in above-mentioned scope, then can obtain the corrosion-resisting pattern that the balance of resist shape, resolution, thermotolerance, adaptation and electrical insulating property is more excellent.
In general formula (V), R 14for hydrogen atom and Y 5for the material of glycidyl can be buied as EXA-7376 series (DIC (strain) system, trade name) business, in addition, R 14for methyl and Y 5for the material of glycidyl can be buied as EPONSU8 series (Mitsubishi Chemical's (strain) system, trade name) business.
There is the bis-phenol phenolic resin varnish type epoxy resin of general formula (IV) and the structural unit represented by (V), such as, the epihalohydrins such as the hydroxyl of following general formula (VIII) and the bis-phenol novolac resin represented by (IX) and chloropropylene oxide can be made respectively to react and obtain.
[changing 7]
In general formula (VIII), R 13with the R in above-mentioned general formula (IV) 13identical, in general formula (IX), R 14with the R in above-mentioned general formula (V) 14identical.
These have the bis-phenol novolac resin of general formula (VIII) and the structural unit represented by (IX), make bisphenol compound and aldehyde compound or ketonic compound react and obtain under the sulfonic acid of preference as having the alkyl of carbon number 1 ~ 4 in molecular structure exists.
Here, as bisphenol compound, as long as the compound with 2 hydroxy phenyls is just not particularly limited, preferably enumerate such as bisphenol-A, bisphenol-ap, bisphenol AF, bisphenol b, bisphenol b P, bisphenol-c, bis-phenol E, Bisphenol F, bis-phenol G, bis-phenol M, bisphenol S, bis-phenol P, bis-phenol TMC, bisphenol Z etc., more preferably bisphenol-A and Bisphenol F.
As the aldehyde compound reacted with above-mentioned bisphenol compound, preferably enumerate formaldehyde, acetaldehyde, benzaldehyde, 4-tolyl aldehyde, 3,4-dimethylbenzaldehydes, biphenyl aldehyde, naphthaldehyde etc., as ketonic compound, preferably enumerate benzophenone, Fluorenone, indone etc.Wherein be preferably formaldehyde.
As the sulfonic acid of alkyl in molecular structure with carbon number 1 ~ 4, preferably enumerate the perfluoroalkane sulfonate etc. that the alkane sulfonic acids such as methane-sulforic acid, ethyl sulfonic acid, propane sulfonic acid, fourth sulfonic acid and paraffin section have fluorine atom.
There is the bis-phenol phenolic resin varnish type epoxy resin of general formula (IV) and the structural unit represented by (V), be more specifically preferably as follows acquisition.
Above-mentioned bisphenol compound and aldehyde compound or ketonic compound are added in reaction vessel, while stir under non-active gas atmosphere, while add sulfonic acid continuously or discontinuously in the mode maintaining 20 ~ 200 DEG C of scopes, bisphenol compound and aldehyde compound or ketonic compound is made to react and obtain thick bis-phenol novolac resin.Then, utilize water-insoluble organic solvent to extract this thick bis-phenol novolac resin, obtain bis-phenol phenolic resin varnish solution, washed, neutralize, and then by this water-insoluble organic solvent distillation removing, obtain bis-phenol phenolic resin varnish type epoxy resin.
Here, as water-insoluble organic solvent, from the viewpoint of improving the operating efficiency extracting, wash, neutralize, preferred boiling point is the solvent of 100 ~ 130 DEG C.As water-insoluble organic solvent, preferably enumerate such as butanols, amylalcohol, methyl cellosolve, ethoxy ethanol, diethylene glycol, methylisobutylketone etc., wherein, more preferably butanols, methyl cellosolve, methylisobutylketone, further preferable methyl isobutyl ketone.
The pH that above-mentioned washing proceeds to thick bis-phenol phenolic resin varnish solution is 3 ~ 7, more preferably pH be 5 ~ 7, the alkaline matters such as NaOH, sodium carbonate, ammonia, triethylene tetramine also can be used as required to neutralize.
Above-mentioned distillation removing is such as preferred heats decompression distillation under being less than or equal to the condition of 3kPa at temperature 170 ~ 200 DEG C, pressure and carries out, and by carrying out in such a situa-tion, can obtain the bis-phenol novolac resin that purity is high.
As epoxy resin (a), excellent and can solvent resistance be improved from the viewpoint of process margin, preferably there is the phenolic resin varnish type epoxy resin of the structural unit represented by general formula (I), there is the epoxy resin of the structural unit represented by general formula (II) and there is the bis-phenol phenolic resin varnish type epoxy resin of the structural unit represented by general formula (IV), more preferably the phenolic resin varnish type epoxy resin represented by general formula (I '), bisphenol A type epoxy resin represented by general formula (II ') or bisphenol f type epoxy resin and there is bis-phenol novolaks A type epoxy resin or the bisphenol f type epoxy resin of the structural unit represented by general formula (IV).
In addition, from the warpage that more can reduce film substrate, and the viewpoint that more can improve resistance to sudden heating is considered, preferably and with the epoxy resin of the structural unit had represented by general formula (IV) and the epoxy resin with the structural unit represented by general formula (V).
(containing vinyl monocarboxylic acid (b))
As with above-mentioned epoxy resin (a) react containing vinyl monocarboxylic acid (b), preferably enumerate the acrylic acid derivatives such as such as acrylic acid, acrylic acid dimer, methacrylic acid, β-furfuryl acrylic acid, β-styrene acrylic, cinnamic acid, crotonic acid, alpha-cyano cinnamic acid, as the half ester compound of hydroxy acryl acid ester and the reaction product of dibasic acid anhydride, as containing vinyl monoglycidyl ether or containing the half ester compound etc. of reaction product of vinyl list ethylene oxidic ester and dibasic acid anhydride.
Half ester compound is by making hydroxy acryl acid ester, reacting containing vinyl monoglycidyl ether or containing vinyl list ethylene oxidic ester and dibasic acid anhydride and obtain with equimolar ratio.These can be used alone a kind or combinationally use two or more containing vinyl monocarboxylic acid (b).
For the synthesis of the hydroxy acryl acid ester of the above-mentioned half ester compound as an example containing vinyl monocarboxylic acid (b), containing vinyl monoglycidyl ether, containing vinyl list ethylene oxidic ester, preferably enumerate such as (methyl) Hydroxyethyl Acrylate, (methyl) hydroxypropyl acrylate, (methyl) hydroxy butyl acrylate, polyethyleneglycol (methyl) acrylate, trimethylolpropane two (methyl) acrylate, pentaerythrite three (methyl) acrylate, dipentaerythritol five (methyl) acrylate, vinyl glycidyl ether, (methyl) glycidyl acrylate etc.
As the dibasic acid anhydride for the synthesis of above-mentioned half ester compound, the dibasic acid anhydride containing saturated base, dibasic acid anhydride containing unsaturated group can be used.As the object lesson of dibasic acid anhydride, preferably enumerate succinic anhydride, maleic anhydride, tetrabydrophthalic anhydride, phthalic anhydride, methyl tetrahydrophthalic anhydride, ethyl tetrabydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, ethyl hexahydrophthalic anhydride, itaconic anhydride etc.
Above-mentioned epoxy resin (a) and containing in the reaction of vinyl monocarboxylic acid (b), preferably react containing the ratio that vinyl monocarboxylic acid (b) is 0.6 ~ 1.05 equivalent with epoxy radicals 1 equivalent relative to epoxy resin (a), more preferably be that the ratio of 0.8 ~ 1.0 equivalent reacts with epoxy radicals 1 equivalent relative to epoxy resin (a) containing vinyl monocarboxylic acid (b), preferably further react containing the ratio that vinyl monocarboxylic acid (b) is 0.9 ~ 1.0 equivalent with epoxy radicals 1 equivalent relative to epoxy resin (a).By reacting with such ratio, optical polymerism improves, and luminous sensitivity is more excellent.
Epoxy resin (a) can by being dissolved in organic solvent by epoxy resin (a) carrying out with containing vinyl monocarboxylic acid (b) with the reaction containing vinyl monocarboxylic acid (b).
As organic solvent, preferably enumerate the such as ketone such as ethyl methyl ketone, cyclohexanone; Toluene, dimethylbenzene, tetramethylbenzene etc. are aromatic hydrocarbon based; The glycol ethers such as methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, DPE, dipropylene glycol diethyl ether, Triethylene glycol ethyl ether; The ester classes such as ethyl acetate, butyl acetate, butyl cellosolve acetate, carbitol acetate; The aliphatic hydrocarbon such as octane, decane; The petroleum solvents etc. such as sherwood oil, naphtha, hydrogenated naphtha, solvent naphtha.
Further, in order to promote that reaction preferably uses catalyzer.As catalyzer, preferably enumerate such as triethylamine, benzylmethylamine, methyl triethyl ammonium chloride, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyl trimethyl methylpyridinium iodide ammonium, triphenylphosphine etc.The use amount of catalyzer is preferably 0.1 ~ 10 mass parts relative to epoxy resin (a) and total 100 mass parts containing vinyl monocarboxylic acid (b).If be set to above-mentioned use amount, then can promote epoxy resin (a) and the reaction containing vinyl monocarboxylic acid (b), therefore preferably.
In order to prevent the polymerization in reaction, preferably use polymerization inhibitor.As polymerization inhibitor, preferably enumerate such as quinhydrones, methylnaphthohydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol etc.The use amount of polymerization inhibitor is preferably 0.01 ~ 1 mass parts relative to epoxy resin (a) and total 100 mass parts containing vinyl monocarboxylic acid (b).If be set to above-mentioned use amount, then the bin stability (pot-life) of composition improves, therefore preferably.In addition, temperature of reaction is preferably 60 ~ 150 DEG C, is more preferably 80 ~ 120 DEG C.
In addition, as required, can will contain the multi-anhydrides such as phenol system compound, trimellitic anhydride, pyromellitic dianhydride, benzophenone tetracarboxylic anhydride, biphenyltetracarboxyacid acid acid anhydride such as vinyl monocarboxylic acid (b) and p-hydroxyphenylethanol and use.
Infer, the epoxy resin (a') obtained thus has the hydroxyl formed by the epoxy radicals of epoxy resin (a) and the addition reaction of the carboxyl containing vinyl monocarboxylic acid (b).
(multi-anhydride (c))
As (A) sour modification containing vinyl epoxy resin, also preferably enumerate the epoxy resin (a ") obtained by making above-mentioned epoxy resin (a') and multi-anhydride (c) react.Infer: at epoxy resin, (in a "), the anhydride group of the hydroxyl (also comprising unborn hydroxyl in epoxy resin (a)) in epoxy resin (a') and multi-anhydride (c) is carried out half-esterification.
As multi-anhydride (c), the multi-anhydride containing saturated base, multi-anhydride containing unsaturated group preferably can be used.As the object lesson of multi-anhydride (c), preferably enumerate succinic anhydride, maleic anhydride, tetrabydrophthalic anhydride, phthalic anhydride, methyl tetrahydrophthalic anhydride, ethyl tetrabydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, ethyl hexahydrophthalic anhydride, itaconic anhydride etc.
In the reaction of epoxy resin (a') with multi-anhydride (c), relative to hydroxyl 1 equivalent in epoxy resin (a'), the multi-anhydride (c) of 0.1 ~ 1.0 equivalent is reacted, thus the acid number of sour modification containing vinyl epoxy resin can be adjusted.
(A) sour modification is preferably 30 ~ 150mgKOH/g containing the acid number of vinyl epoxy resin, is more preferably 40 ~ 120mgKOH/g, more preferably 50 ~ 100mgKOH/g.If acid number is more than or equal to 30mgKOH/g, then the dissolubility of photosensitive polymer combination in dilute alkaline soln not easily reduces, if be less than or equal to 150mgKOH/g, then the electrical specification of cured film not easily reduces.
Epoxy resin (a') is preferably 60 ~ 120 DEG C with the temperature of reaction of multi-anhydride (c).
In addition, as required, as epoxy resin (a), such as also can and use a part of bisphenol-A epoxy resin.Further, as (A) sour modification containing vinyl epoxy resin, also can and with styrene-maleic acid system resins such as (methyl) Hydroxyethyl Acrylate modifiers of a part of styrene-maleic anhydride copolymer.
(A) sour modification is preferably 3000 ~ 30000 containing the weight-average molecular weight of vinyl epoxy resin, is more preferably 4000 ~ 25000, and more preferably 5000 ~ 18000.If (A) weight-average molecular weight of composition is in above-mentioned scope, then can obtain the pattern that the balance of resist shape, resolution, thermotolerance, adaptation and electrical insulating property is more excellent.Here, weight-average molecular weight utilizes weight-average molecular weight that measured as gel permeation chromatography (GPC) method of solvent by tetrahydrofuran, polyethylene conversion.More specifically, such as, can measure with following GPC determinator and condition determination, and use value that the typical curve of polystyrene standard converts as weight-average molecular weight.In addition, for the making of typical curve, use 5 sample sets (" PStQuickMP-H " and " PStQuickB ", eastern Cao (strain) makes) as polystyrene standard.
(GPC determinator)
GPC device: high speed GPC device " HCL-8320GPC ", detecting device is differential refractometer, and eastern Cao (strain) makes
Post: ColumnTSKgelSuperMultiporeHZ-H (column length: 15cm, column internal diameter: 4.6mm), eastern Cao (strain) makes
(condition determination)
Solvent: tetrahydrofuran (THF)
Measure temperature: 40 DEG C
Flow: 0.35ml/ minute
Sample solution concentration: 10mg/THF5ml
Injection rate IR: 20 μ l
As (A) sour modification containing vinyl epoxy resin, preferably make the phenolic resin varnish type epoxy resin of the structural unit had represented by general formula (I), be preferably the phenolic resin varnish type epoxy resin represented by general formula (I '), or there is the epoxy resin of the structural unit represented by general formula (II), be preferably bisphenol A type epoxy resin represented by general formula (II ') and bisphenol f type epoxy resin and contain vinyl monocarboxylic acid (b) and react and the epoxy resin (a ') that obtains, and the epoxy resin this epoxy resin (a ') being reacted with the multi-anhydride (c) containing saturated base or unsaturated group and obtains (a "), more preferably epoxy resin (a ").
These epoxy resin (a ') and (a ") can be used alone a kind or combinationally use two or more, and preferred compositions is multiple to be used.As combination, the combination of epoxy resin that epoxy resin that the phenolic resin varnish type epoxy resin preferably represented by general formula (I ') obtains (a ') or (a ") obtain with the bisphenol A type epoxy resin represented by general formula (II ') and bisphenol f type epoxy resin (a ') or (a ") two kinds, more preferably the combination that epoxy resin that epoxy resin that the phenolic resin varnish type epoxy resin represented by general formula (I ') obtains (a ") obtains with the bisphenol A type epoxy resin represented by general formula (II ') and bisphenol f type epoxy resin (a ") is two kinds.
The mass mixing ratio of epoxy resin that epoxy resin that the phenolic resin varnish type epoxy resin represented by general formula (I ') obtains (a ') or (a ") obtain with the bisphenol A type epoxy resin represented by general formula (II ') and bisphenol f type epoxy resin (a ') or (a ") is preferably 95:5 ~ 30:70, be more preferably 90:10 ~ 40:60, more preferably 80:20 ~ 45:55.
In addition, when (C5) sulfur-bearing alcohol-based compounds stated after a procedure is as (C) composition, the combination of epoxy resin that the epoxy resin that preferably obtained by the bis-phenol phenolic resin varnish type epoxy resin of the structural unit had represented by general formula (IV) (a ') or (a ") obtain with the bisphenol A type epoxy resin represented by general formula (II ') and bisphenol f type epoxy resin (a ') or (a ") two kinds, more preferably the combination that epoxy resin that the epoxy resin that obtained by bis-phenol novolaks A type epoxy resin or the bisphenol f type epoxy resin of the structural unit had represented by general formula (IV) (a ") obtains with the bisphenol A type epoxy resin represented by general formula (II ') and bisphenol f type epoxy resin (a ") is two kinds.
The mass mixing ratio of epoxy resin that the epoxy resin that obtained by the bis-phenol phenolic resin varnish type epoxy resin of the structural unit had represented by general formula (IV) (a ') or (a ") obtain with the bisphenol A type epoxy resin represented by general formula (II ') and bisphenol f type epoxy resin (a ') or (a ") is preferably 90:10 ~ 30:70, be more preferably 80:20 ~ 40:60, more preferably 70:30 ~ 50:50.
Solid constituent total amount in photosensitive polymer combination is set to 100 mass parts, and the content of (A) composition is preferably 20 ~ 80 mass parts, is more preferably 30 ~ 75 mass parts, is particularly preferably 40 ~ 75 mass parts.If (A) content of composition is in above-mentioned scope, then can obtain the more excellent film of thermotolerance, electrical specification and chemical reagent resistance.Here, the solid constituent total amount of present embodiment refers to the total amount of the solid constituent contained by (A) ~ (F) composition.Such as, when the photosensitive polymer combination of present embodiment comprises (A) ~ (D) composition, (A) total amount of the solid constituent ~ (D) contained by composition is solid constituent total amount, in addition when the photosensitive polymer combination of present embodiment comprises (A) ~ (E) composition, (A) total amount of the solid constituent ~ (E) contained by composition is solid constituent total amount, in addition, under the photosensitive polymer combination of present embodiment comprises (A) ~ (F) composition situation, (A) total amount of the solid constituent ~ (F) contained by composition is solid constituent total amount.
< (B) acylphosphine oxide system Photoepolymerizationinitiater initiater >
The photosensitive polymer combination of present embodiment comprises acylphosphine oxide system Photoepolymerizationinitiater initiater as (B) composition.
As (B) acylphosphine oxide system Photoepolymerizationinitiater initiater, as long as the Photoepolymerizationinitiater initiater with acylphosphine oxide base (=P (=O)-C (=O)-Ji) is just not particularly limited, preferably enumerate such as (2, 6-Dimethoxybenzoyl)-2, 4, 6-trimethylbenzoyl-amyl group phosphine oxide, two (2, 4, 6-trimethylbenzoyl)-phenylphosphine oxide, 2, 4, 6-trimethylbenzoyldiphenyl oxide, ethyl-2, 4, 6-trimethylbenzoyl phenyl phosphinate, two (2, 4, 6-trimethylbenzoyl)-phenylphosphine oxide, (2, 5-dihydroxy phenyl) diphenyl phosphine oxide, (p-hydroxybenzene) diphenyl phosphine oxide, two (p-hydroxybenzene) phenylphosphine oxide and three (p-hydroxybenzene) phosphine oxide etc., can be used alone or in combination of two or more.
Solid constituent total amount in photosensitive polymer combination is set to 100 mass parts, and the content of (B) acylphosphine oxide system Photoepolymerizationinitiater initiater is preferably 0.2 ~ 15 mass parts.If be more than or equal to 0.2 mass parts, then exposure portion not easily stripping in development, if be less than or equal to 15 mass parts, then thermotolerance not easily reduces.In addition, from the same reason, the content of (B) Photoepolymerizationinitiater initiater is more preferably 0.2 ~ 10 mass parts, more preferably 0.2 ~ 5 mass parts, is particularly preferably 0.5 ~ 5 mass parts, is extremely preferably 0.5 ~ 3 mass parts.
In addition, can by N, the photopolymerization such as tertiary amines such as N-dimethyl amino benzoate, N, N-dimethylaminobenzoic acid isopentyl ester, amyl group-4-dimethylaminobenzoic acid ester, triethylamine, triethanolamine causes auxiliary agent and is used alone a kind or combinationally use two or more.
< (C) adjuvant >
The photosensitive polymer combination of present embodiment contains and is selected from least one in following material as (C) composition: (C1) alkyl amino benzene derivative, (C2) pyrazoline system sensitizer or anthracene system sensitizer, (C3) imidazoles system Photoepolymerizationinitiater initiater is selected from, at least one Photoepolymerizationinitiater initiater in acridine system Photoepolymerizationinitiater initiater and two luxuriant titanium system Photoepolymerizationinitiater initiaters, (C4) hindered phenol system antioxidant is selected from, quinone system antioxidant, amine system antioxidant, at least one antioxidant in sulphur system antioxidant and phosphorous antioxidant, and (C5) sulfur-bearing alcohol-based compounds.By by these adjuvants and (B) acylphosphine oxide system's Photoepolymerizationinitiater initiater and use, can obtain that the rectilinearity that can form pattern contour is good and resist shape excellent, the photosensitive polymer combination of the pattern of excellent in resolution.
((C1) alkyl amino benzene derivative)
(C1) be just not particularly limited as long as alkyl amino benzene derivative has alkyl amino on phenyl ring, it effectively plays a role as hydrogen donor, can more improve photosensitive polymer combination luminous sensitivity and through day stability.Here, hydrogen donor refers to the free radical produced for the exposure-processed by above-mentioned Photoepolymerizationinitiater initiater, can provide the compound of hydrogen atom.In present embodiment, above-mentioned (B) acylphosphine oxide system optical polymerism initiating agent and the combination as (C1) alkyl amino benzene derivative of hydrogen donor especially the rectilinearity forming pattern contour is good and resist shape excellent, be effective in the pattern of excellent in resolution.
As (C1) alkyl amino benzene derivative, preferably enumerate such as phenylglycine derivatives, aminobenzoic acid derivative, aminobenzoic acid ester derivant etc.
As phenylglycine derivatives, preferably enumerate N-phenylglycine, N, N-diphenyl glycine, N-naphthyl glycocoll etc.
As aminobenzoic acid derivative, preferably enumerate 2-methylaminobenzoate, 2-ethylamino benzoic acid etc.In addition, as aminobenzoic acid ester derivant, preferably enumerate N, N-dimethyl amino benzoate, N, N-diethylamino ethyl benzoate, N, N-dimethylaminobenzoic acid isopentyl ester, N, N-diethylamino isoamyl benzoate etc.
In present embodiment, the aromatic amines compound with alkyl amino can be used.As concrete example, the carbon number preferably enumerating such as alkyl is the dialkyl group diphenylamine of 8 ~ 14, octylatcd diphenylamine, 4,4 '-bis-(α, α-dimethylbenzyl) diphenylamine, N-phenyl-N '-isopropyl-to aniline, N-phenyl-N '-(1,3-dimethylbutyl)-to aniline and N-phenyl-N '-(3-methacryloxy-2-hydroxypropyl)-to aniline etc.
In these (C1) alkyl amino benzene derivatives, preferred N-phenylglycine, 2-methylaminobenzoate and N, N-diethylamino ethyl benzoate.
These (C1) alkyl amino benzene derivatives can be used alone or in combination of two or more.In addition, aliphatic amine compound can be used with abovementioned alkyl aminophenyl derivative simultaneously.As concrete example, preferably enumerate such as triethanolamine, triethylamine etc.
Solid constituent total amount in photosensitive polymer combination is set to 100 mass parts, (C1) content of alkyl amino benzene derivative is preferably 0.01 ~ 5 mass parts, be more preferably 0.1 ~ 3 mass parts, more preferably 0.2 ~ 1.5 mass parts, be particularly preferably 0.2 ~ 1.0 mass parts.If this content is more than or equal to 0.1 mass parts, then the solution of photosensitive polymer combination not easily gelation, if be less than or equal to 5 mass parts, then luminous sensitivity not easily reduces, therefore preferably.
((C2) pyrazoline system's sensitizer or anthracene system sensitizer)
(C2) composition is pyrazoline system sensitizer or anthracene system sensitizer.By adding (C2) pyrazoline system sensitizer, even if be digit explosure, also can obtain the disappearance that do not produce the undercutting that is cut off of bottom and resist top and can form that the rectilinearity of pattern contour is good and resist shape is excellent, the photosensitive polymer combination of the pattern of excellent in resolution.
As (C2) pyrazoline system sensitizer, as long as the sensitizer with pyrazole ring is just not particularly limited, the pyrazoline system sensitizer represented by preferred following general formula (VI).
[changing 8]
In general formula (VI), R represents the alkyl of carbon number 4 ~ 12, and a, b and c represent the integer of 0 ~ 2 respectively, and the summation of a, b and c is 1 ~ 6.When the summation of a, b and c is 2 ~ 6, can be the same or different respectively with the multiple R in a part.The alkyl of R can be straight-chain also can be branched, in addition can by replacements such as halogen atom, alkyl, aryl, aralkyl, amino, amide group, alkoxys.As R, the alkyl of preferred carbon number 4,8 and 12, more specifically, preferred normal-butyl, the tert-butyl group, tertiary octyl group and dodecyl, the identical or different group preferably selected from these.
As such pyrazoline system sensitizer, preferably enumerate 1-(4-tbutyl-phenyl)-3-styryl-5-phenyl-pyrazole quinoline, 1-phenyl-3-(4-tert-butyl-styrene base)-5-(4-tbutyl-phenyl)-pyrazoline, 1, 5-pair-(4-tbutyl-phenyl)-3-(4-tert-butyl-styrene base)-pyrazoline, 1-(the tertiary Octyl-phenyl of 4-)-3-styryl-5-phenyl-pyrazole quinoline, 1-phenyl-3-(the tertiary octyl group-styryl of 4-)-5-(the tertiary Octyl-phenyl of 4-)-pyrazoline, 1, 5-pair-(the tertiary Octyl-phenyl of 4-)-3-(the tertiary octyl group-styryl of 4-)-pyrazoline, 1-(4-dodecyl-phenyl)-3-styryl-5-phenyl-pyrazole quinoline, 1-phenyl-3-(4-dodecyl-styryl)-5-(4-dodecyl-phenyl)-pyrazoline, 1-(4-dodecyl-phenyl)-3-(4-dodecyl-styryl)-5-(4-dodecyl-phenyl)-pyrazoline, 1-(the tertiary Octyl-phenyl of 4-)-3-(4-tert-butyl-styrene base)-5-(4-tbutyl-phenyl)-pyrazoline, 1-(4-tbutyl-phenyl)-3-(the tertiary octyl group-styryl of 4-)-5-(the tertiary Octyl-phenyl of 4-)-pyrazoline, 1-(4-dodecyl-phenyl)-3-(4-tert-butyl-styrene base)-5-(4-tbutyl-phenyl)-pyrazoline, 1-(4-tbutyl-phenyl)-3-(4-dodecyl-styryl)-5-(4-dodecyl-phenyl)-pyrazoline, 1-(4-dodecyl-phenyl)-3-(the tertiary octyl group-styryl of 4-)-5-(the tertiary Octyl-phenyl of 4-)-pyrazoline, 1-(the tertiary Octyl-phenyl of 4-)-3-(4-dodecyl-styryl)-5-(4-dodecyl-phenyl)-pyrazoline, 1-(2, 4-di-n-butyl-phenyl)-3-(4-dodecyl-styryl)-5-(4-dodecyl-phenyl)-pyrazoline, 1-phenyl-3-(3, 5-di-t-butyl-styryl)-5-(3, 5-di-t-butyl-phenyl)-pyrazoline, 1-phenyl-3-(2, 6-di-t-butyl-styryl)-5-(2, 6-di-t-butyl-phenyl)-pyrazoline, 1-phenyl-3-(2, 5-di-t-butyl-styryl)-5-(2, 5-di-t-butyl-phenyl)-pyrazoline, 1-phenyl-3-(2, 6-di-n-butyl-styryl)-5-(2, 6-di-n-butyl-phenyl)-pyrazoline, 1-(3, 4-di-t-butyl-phenyl)-3-styryl-5-phenyl-pyrazole quinoline, 1-(3, 5-di-t-butyl-phenyl)-3-styryl-5-phenyl-pyrazole quinoline, 1-(4-tbutyl-phenyl)-3-(3, 5-di-t-butyl-styryl)-5-(3, 5-di-t-butyl-phenyl)-pyrazoline and 1-(3, 5-di-t-butyl-phenyl)-3-(3, 5-di-t-butyl-styryl)-5-(3, 5-di-t-butyl-phenyl)-pyrazoline etc.
Solid constituent total amount in photosensitive polymer combination is set to 100 mass parts, (C2) content of pyrazoline system sensitizer is preferably 0.01 ~ 10.0 mass parts, be more preferably 0.01 ~ 5 mass parts, more preferably 0.02 ~ 1 mass parts, be particularly preferably 0.03 ~ 0.5 mass parts, be extremely preferably 0.03 ~ 0.2 mass parts.If (C2) content of pyrazoline system sensitizer is more than or equal to 0.01 mass parts, then exposure portion not easily stripping in development, if be less than or equal to 10 mass parts, then can suppress the reduction of thermotolerance.
The photosensitive polymer combination of present embodiment preferably adds (C2) anthracene system sensitizer.
(C2) anthracene system sensitizer used in the photosensitive polymer combination of present embodiment by improving photo-curable, thus can form the pattern of resist shape excellence, excellent in resolution.
As (C2) anthracene system sensitizer, preferably enumerate the compound such as represented by following general formula (XI).
[changing 9]
In general formula (XI), l 11be the integer of 1 ~ 10, R 3represent the thiazolinyl of the alicyclic group of the alkyl of hydrogen atom, carbon number 1 ~ 8, carbon number 3 ~ 20, carbon number 2 ~ 8, aryl, heteroaryl or-N (R 4) 2base, the R of more than 2 3can be bonded to each other and form ring texture, this ring texture can contain heteroatoms, alkyl, thiazolinyl can be straight-chain in addition also can be branched, in addition can also by replacements such as halogen atom, alkyl, aryl, aralkyl, amino, amide group, alkoxys.In addition, multiple R 3, R 4can be the same or different.
X represents singly-bound, oxygen atom, sulphur atom, carbonyl, sulfonyl ,-N (R ')-Ji ,-C (=O)-O-base ,-C (=O)-S-base ,-SO 2-O-base ,-SO 2-S-base ,-SO 2-N (R ')-Ji ,-O-CO-base ,-S-C (=O)-Ji ,-O-SO 2-Ji or-S-SO 2-Ji.But X is singly-bound and R 3for hydrogen atom combination (namely without replace anthracene) except.In addition, multiple X can be the same or different.
Here, R 4represent the thiazolinyl of the alicyclic group of the alkyl of hydrogen atom, carbon number 1 ~ 8, carbon number 3 ~ 20, carbon number 2 ~ 8, aryl or heteroaryl, R 4can be combined with each other each other and form ring texture, this ring texture can contain heteroatoms, alkyl, thiazolinyl can be straight-chain also can be branched, in addition can also by replacements such as halogen atom, alkyl, aryl, aralkyl, amino, amide group, alkoxys.
As above-mentioned R 3and R 4in the alicyclic group of carbon number 3 ~ 20, except cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, also preferably enumerate the bridge joint ester ring type alkyl etc. of the carbon numbers 6 ~ 20 such as such as norborny, three ring decyls, tetracyclododecyl group, adamantyl, methyl adamantane base, ethyl adamantyl and butyl adamantyl.
As aryl, preferably enumerate as R 13the group illustrated in aryl, as heteroaryl, preferably enumerate and more than of arbitrary annular atoms forming these aryl be substituted by the heteroatomss such as sulphur atom, oxygen atom, nitrogen-atoms and the group that obtains.
As above-mentioned R 3and R 4, preferably enumerate such as hydrogen atom, methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, the tert-butyl group, n-pentyl, n-hexyl, n-pentyl, n-octyl, cyclopentyl, cyclohexyl, camphoroyl base, norborny, p-methylphenyl, benzyl, phenyl and 1-naphthyl etc.
In addition, as (C2) anthracene system sensitizer represented by above-mentioned general formula (XI), the alkyl anthracenes such as such as 1-methylanthracene, 2-methyl anthracene, 2-ethyl anthracene, 2-tert-butyl anthracene, 9-methyl anthracene are preferably enumerated; The dialkyl group anthracenes such as 9,10-dimethylanthracene, 9,10-dipropyl anthracenes, 9,10-dibutyl anthracenes; The hydroxy alkyl anthracenes such as 9-(hydroxymethyl) anthracene, 9-(2-hydroxyethyl) anthracene; The dialkoxy anthracenes such as 9,10-diethoxy anthracene, 9,10-dipropoxy anthracenes, 9,10-dibutoxy anthracenes, 9,10-bis-(2-ethyl hexyl oxy) anthracene; The thiazolinyl anthracenes such as 9-vinyl anthracene, 9-allyl anthracene; The amino anthracenes such as 1-amino anthracene, 2-amino anthracene, 9-(Methylaminomethyl) anthracene; The anthracene aldehyde such as 9-anthracene aldehyde, 10-methyl-9-anthracene aldehyde; And 9-phenylanthracene, 9-acetyl anthracene, 9,10-diphenylanthrancenes, 1,2-benzene first anthracene, 1,8,9-triacetoxyl group anthracene, Isosorbide-5-Nitrae, 9,10-tetrahydroxy anthracenes etc., these anthracene system sensitizers can be used alone or in combination of two or more
Wherein, preferred diphenylanthrancene, dialkyl group anthracene and dialkoxy anthracene, more preferably 9,10-dimethylanthracene, 9,10-diphenylanthrancenes, 9,10-diethoxy anthracenes, 9,10-dipropoxy anthracene, 9,10-dibutoxy anthracenes and 9,10-bis-(2-ethyl hexyl oxy) anthracene, further preferably 9,10-diethoxy anthracene, 9,10-dipropoxy anthracenes, 9,10-dibutoxy anthracenes and 9,9, the 10-dialkoxy anthracenes such as 10-bis-(2-ethyl hexyl oxy) anthracene.In present embodiment, if use these anthracene system sensitizers, then can obtain the photosensitive polymer combination especially radioactive ray of wavelength 300 ~ 450nm to luminous sensitivity, can improve photo-curable, therefore, it is possible to formed, resist shape is excellent, the pattern of excellent in resolution.
Solid constituent total amount in photosensitive polymer combination is set to 100 mass parts, and the content of (C2) anthracene system sensitizer is preferably 0.001 ~ 10 mass parts.(C2) when the content of anthracene system sensitizer is in above-mentioned scope, can improve photo-curable, therefore, it is possible to formed, resist shape is excellent, the pattern of excellent in resolution.From the same reason, the content of (C2) anthracene system sensitizer is more preferably 0.01 ~ 5 mass parts, and more preferably 0.03 ~ 3 mass parts, is particularly preferably 0.1 ~ 1.5 mass parts.
In addition, as relative to (A) sour modification containing vinyl epoxy resin 100 mass parts, the content of (C2) anthracene system sensitizer, be preferably 0.001 ~ 10 mass parts, be more preferably 0.01 ~ 5 mass parts, more preferably 0.03 ~ 3 mass parts.
((C3) is selected from least one Photoepolymerizationinitiater initiater in imidazoles system Photoepolymerizationinitiater initiater, acridine system Photoepolymerizationinitiater initiater and two luxuriant titanium system Photoepolymerizationinitiater initiaters)
(C3) composition is selected from least one Photoepolymerizationinitiater initiater in imidazoles system Photoepolymerizationinitiater initiater, acridine system Photoepolymerizationinitiater initiater and two luxuriant titanium system Photoepolymerizationinitiater initiaters.
In present embodiment, the combination of above-mentioned (B) acylphosphine oxide system optical polymerism initiating agent and (C3) composition especially the rectilinearity forming pattern contour well and resist shape is excellent, effective in the pattern of excellent in resolution.
As imidazoles system Photoepolymerizationinitiater initiater, as long as the Photoepolymerizationinitiater initiater in molecule with imidazole ring is just not particularly limited, preferably enumerate 2, 2 '-bis-(Chloro-O-Phenyl)-4, 5, 4 ', 5 '-tetraphenyl-1, 2 '-bisglyoxaline, and 2-(Chloro-O-Phenyl)-4, 5-diphenyl-imidazole dimer, 2-(Chloro-O-Phenyl)-4, 5-bis-(m-methoxyphenyl) imidazoles dimer, 2-(adjacent fluorophenyl)-4, 5-diphenyl-imidazole dimer, 2-(o-methoxyphenyl)-4, 5-diphenyl-imidazole dimer, 2-(p-methoxyphenyl)-4, 5-diphenyl-imidazole dimer, 2, 4-bis-(p-methoxyphenyl)-5-phenylimidazole dimer, 2-(2, 4-Dimethoxyphenyl)-4, 5-diphenyl-imidazole dimer and 2-(to methyl mercapto phenyl)-4, 5-diphenyl-imidazole dimer etc. 2, 4, 5-triarylimidazoles dimer etc.
In 2,4,5-triarylimidazoles dimer, form these dimeric 22,4,5-triarylimidazoles and can have identical structure respectively, also can have different structures.That is, the triaryl kind in 2,4,5-triarylimidazoles dimers can be the same or different.
As such 2, 4, 5-triarylimidazoles dimer, preferably enumerate such as 2, 2 '-bis-(Chloro-O-Phenyl)-4, 5, 4 ', 5 '-tetraphenyl-1, 2 '-bisglyoxaline, 2-(Chloro-O-Phenyl)-4, 5-diphenyl-imidazole dimer, 2, 2 '-bis-(Chloro-O-Phenyl)-4, 4 ', 5, 5 '-four (rubigan) imidazoles dimer, 2-(Chloro-O-Phenyl)-4, 5-bis-(m-methoxyphenyl) imidazoles dimer, 2, 2 '-bis-(Chloro-O-Phenyl)-4, 4 ', 5, 5 '-four (to fluorophenyl) imidazoles dimer, 2, 2 '-bis-(o-bromophenyl)-4, 4 ', 5, 5 '-four (to chlorine p-methoxyphenyl) imidazoles dimer, 2, 2 '-bis-(Chloro-O-Phenyl)-4, 4 ', 5, 5 '-four is (adjacent, p-dichlorophenyl) imidazoles dimer, 2, 2 '-bis-(Chloro-O-Phenyl)-4, 4 ', 5, 5 '-four is (adjacent, p-dibromo phenyl) imidazoles dimer, 2, 2 '-bis-(Chloro-O-Phenyl)-4, 4 ', 5, 5 '-four (to chloronaphthyl, methylnaphthyl) imidazoles dimer, 2, 2 '-bis-(, p-dichlorophenyl)-4, 4 ', 5, 5 '-tetraphenyl imidazoles dimer, 2, 2 '-bis-(adjacent, Dui ー dichlorophenyl)-4, 4 ', 5, 5 '-tetraphenyl imidazoles dimer, 2, 2 '-bis-(adjacent, p-dichlorophenyl)-4, 4 ', 5, 5 '-four is (adjacent, p-dichlorophenyl) imidazoles dimer, 2-(adjacent fluorophenyl)-4, 5-diphenyl-imidazole dimer, 2-(o-methoxyphenyl)-4, 5-diphenyl-imidazole dimer, 2-(p-methoxyphenyl)-4, 5-diphenyl-imidazole dimer, 2, 4-bis-(p-methoxyphenyl)-5-phenylimidazole dimer, 2-(2, 4-Dimethoxyphenyl)-4, 5-diphenyl-imidazole dimer, 2-(to methyl mercapto phenyl)-4, 5-diphenyl-imidazole dimer, 2, 2 '-bis-(to bromophenyl)-4, 4 ', 5, 5 '-tetraphenyl imidazoles dimer, 2, 2 '-bis-(o-bromophenyl)-4, 4 ', 5, 5 '-four is (adjacent, p-dichlorophenyl) imidazoles dimer, 2, 2 '-bis-(o-bromophenyl)-4, 4 ', 5, 5 '-four (to iodophenyl) imidazoles dimer, 2, 2 '-bis-(bromophenyl)-4, 4 ', 5, 5 '-tetraphenyl imidazoles dimer, 2, 2 '-bis-(, p-dibromo phenyl)-4, 4 ', 5, 5 '-tetraphenyl imidazoles dimer etc.
These are 2 years old, 4, the dimeric aryl of 5-triarylimidazoles can further by halogen atom, the alkyl of carbon number 1 ~ 20, the naphthenic base of carbon number 3 ~ 10, the aryl of carbon number 6 ~ 14, amino, the alkyl amino of carbon number 1 ~ 10, nitro, cyano group, sulfydryl, the alkyl thiol of carbon number 1 ~ 10, the dialkyl amido of carbon number 2 ~ 20, allyl, the hydroxy alkyl of carbon number 1 ~ 20, the carbon number of alkyl is the carboxyalkyl of 1 ~ 10, the carbon number of alkyl is the acyl group of 1 ~ 10, the alkoxy of carbon number 1 ~ 20 or containing replacements such as heterocyclic radicals.
As acridine system Photoepolymerizationinitiater initiater, as long as the Photoepolymerizationinitiater initiater in molecule with acridine ring is just not particularly limited, preferably enumerate 1, two-β-(acridine-9-base) acrylate of 4-butylidene, terephthaldehyde's base two (β-(acridine-9-base) acrylate), two (β-(acridine-9-base) acrylate, the 9-phenylacridine, 1 of triethylene glycol, two (9,9 '-acridinyl) heptane of 7-etc.
As two luxuriant titanium system Photoepolymerizationinitiater initiaters, as long as the Photoepolymerizationinitiater initiater as metal with the metallocene compound of titanium is just not particularly limited, preferably enumerate two (η 5-cyclopentadienyl group)-bis-(the fluoro-3-of 2,6-bis-(1H-pyrroles-1-base) phenyl) titanium, two (2,4-cyclopentadienyl group)-bis-(the fluoro-3-of 2,6-bis-(1-pyrrole radicals) phenyl) titanium etc.These Photoepolymerizationinitiater initiaters can be used alone or in combination of two or more.
Solid constituent total amount in photosensitive polymer combination is set to 100 mass parts, (C3) content of Photoepolymerizationinitiater initiater is preferably 0.01 ~ 15 mass parts, be more preferably 0.01 ~ 5 mass parts, more preferably 0.01 ~ 3.5 mass parts, be particularly preferably 0.02 ~ 1.0 mass parts.If this content is more than or equal to 0.01 mass parts, then the solution of photosensitive polymer combination not easily gelation, if be less than or equal to 15 mass parts, then luminous sensitivity not easily reduces, therefore preferably.
Solid constituent total amount in photosensitive polymer combination is set to 100 mass parts, and (B) acylphosphine oxide system Photoepolymerizationinitiater initiater is preferably 0.2 ~ 15 mass parts with the total content of (C3) Photoepolymerizationinitiater initiater.If be more than or equal to 0.2 mass parts, then exposure portion not easily stripping in development, if be less than or equal to 15 mass parts, then thermotolerance not easily reduces.In addition, from the same reason, (B) Photoepolymerizationinitiater initiater is more preferably 0.2 ~ 10 mass parts, more preferably 0.2 ~ 5 mass parts with the total content of (C3) Photoepolymerizationinitiater initiater, be particularly preferably 0.5 ~ 5 mass parts, be extremely preferably 0.5 ~ 3 mass parts.
Above-mentioned (B) acylphosphine oxide system optical polymerism initiating agent is preferably 100:0.5 ~ 100:8 with the mass ratio of (C3) Photoepolymerizationinitiater initiater, is more preferably 100:1 ~ 100:6, more preferably 100:1 ~ 100:5.When mass ratio is in above-mentioned scope, there is resist shape excellent, the tendency that bottom curability, aperture precision improve, therefore preferably.
((C4) is selected from least one antioxidant in hindered phenol system antioxidant, quinone system antioxidant, amine system antioxidant, sulphur system antioxidant and phosphorous antioxidant)
(C4) composition is selected from least one antioxidant in hindered phenol system antioxidant, quinone system antioxidant, amine system antioxidant, sulphur system antioxidant and phosphorous antioxidant.
By using (C4) composition, the pattern that can form resist shape excellence, excellent in resolution can be obtained, can be formed and there is excellent solder heat resistance and the photosensitive polymer combination of the corrosive pattern of resistance to solder flux.
As hindered phenol system antioxidant, preferably enumerate pentaerythrite four [3-(3, 5-di-tert-butyl-hydroxy phenyl) propionic ester] (BASF Japan (strain) makes, IRGANOX1010 (trade name)), two [the 3-(3 of thiodiethylene, 5-di-tert-butyl-hydroxy phenyl) propionic ester] (BASF Japan (strain) makes, IRGANOX1035 (trade name)), octadecyl [3-(3, 5-di-tert-butyl-hydroxy phenyl) propionic ester] (BASF Japan (strain) makes, IRGANOX1076 (trade name)), octyl group 1-3, (BASF Japan (strain) makes 5-di-t-butyl-4-hydroxyl-hydrogen cinnamic acid, IRGANOX1135 (trade name)) and 4, (BASF Japan (strain) makes 6-two (pungent butylthiomethyl-orthoresol), the commercially available product such as IRGANOX1520L), and n-octadecane base-3-(3 ' 5 '-di-t-butyl-4 '-hydroxy phenyl)-propionic ester, n-octadecane base-3-(3 '-methyl-5 '-the tert-butyl group-4 '-hydroxy phenyl)-propionic ester, n-tetradecane base-3-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl)-propionic ester, 1, 6-hexanediol-bis--(3-(3, 5-di-tert-butyl-hydroxy phenyl)-propionic ester), 1, 4-butylene glycol-bis--(3-(3, 5-di-tert-butyl-hydroxy phenyl)-propionic ester), triethylene glycol-bis--(3-(the 3-tert-butyl group-5-methyl-4-hydroxy phenyl)-propionic ester), four-(methylene-3-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionate methane, 3, two (the 2-(3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxy)-1 of 9-, 1-dimethyl ethyl) 2, 4, 8, 10-tetra-oxaspiro (5, 5) undecane, N, N '-bis--3-(3 ' 5 '-di-t-butyl-4-hydroxyl phenol) propiono hexamethylene diamine, N, two-the 3-of N '-tetramethylene (3 '-methyl-5 '-tertiary butyl-4-hydroxy phenol) propiono diamines, N, N '-bis--(3-(3, 5-di-t-butyl-4-hydroxyl phenol) propiono) hydrazine, N-salicyl-N '-salicylidene hydrazine, 3-(N-salicyl) amino-1, 2, 4-triazole and N, N '-bis-(2-(3-(3, 5-dibutyl-4-hydroxy phenyl) propionyloxy) ethyl) oxygen base acid amides etc., they can be used alone or in combination of two or more.In addition, as quinone system antioxidant, preferably enumerate the quinone system antioxidants etc. such as quinhydrones, TBHQ, Hydroquinone monomethylether, first quinone, benzo quinone, they can be used alone or in combination of two or more.These antioxidants with phenolic hydroxyl group can expect the seizure effect of peroxylradicals (ROO), alkyl diradical (R) etc.
As amine system antioxidant, preferably enumerate phenyl naphthyl amines, 4,4 '-dimethoxydiphenyl amine, 4,4 '-bis-(α, α-dimethylbenzyl) diphenylamine, di-t-butyl diphenylamine, N, N '-two (octyl phenyl) amine, 4-isopropoxydiphenylamine, N, N '-two (2-naphthyl)-to aniline, two (2,2,6,6-tetramethyl-4-piperidyl)-sebacate, phenothiazine etc., they can be used alone or in combination of two or more.Amine system antioxidant can expect the seizure effect of peroxylradicals (ROO).
As sulphur system antioxidant, preferably enumerate two dodecyl-3, 3 '-thiodipropionate, two myristyl-3, 3 '-thiodipropionate, two octadecyl-3, 3 '-thiodipropionate, double tridecyl-3, 3 '-thiodipropionate, pentaerythrite four (3-laurylthiopropionate), pentaerythrite four (3-TTP ester), pentaerythrite four (3-tridecyl thiopropionate), dilauryl-3, 3-thiodipropionate, myristyl-3, 3-thiodipropionate, distearyl-3, 3-thiodipropionate, pentaerythrite four (3-lauryl thiodipropionate, 2-mercaptobenzimidazole, lauryl stearyl-thio dipropionate, the zinc salt of 2 mercaptomethyl benzimidazole, the zinc salt of 2-mercaptobenzimidazole, 2 mercaptomethyl benzimidazole, dibutyl zinc thiocarbamate etc., they can be used alone or in combination of two or more.
As phosphorous antioxidant, preferably enumerate triphenyl phosphite, three (aminomethyl phenyl) phosphite ester, tri iso octyl phosphorite, tridecyl phosphite, three (2-ethylhexyl) phosphite ester, three (nonyl phenyl) phosphite ester, three (octyl phenyl) phosphite ester, three [decyl gathers (oxygen ethene) phosphite ester, three (cyclohexyl phenyl) phosphite ester, thricyclohexyl phosphite ester, three (decyl) thiophosphite, three isodecyl thiophosphites, phenyl-bis-(2-ethylhexyl) phosphite ester, phenyl-diiso decyl phosphite ester, four decyls gather (oxygen ethene)-bis-(ethylphenyl) phosphate, phenyl-dicyclohexyl phosphite ester, phenyl-diisooctyl phosphite ester, phenyl-two (tridecyl) phosphite ester, diphenyl-cyclohexyl phosphite ester, diphenyl-iso-octyl phosphite ester, diphenyl-2-ethylhexyl phosphite ester, diphenyl-isodecyl phosphite, diphenyl-cyclohexyl phenyl phosphite ester, they can be used alone or in combination of two or more by diphenyl-(tridecyl) thiophosphites etc.
As sulphur system antioxidant and phosphorous antioxidant, the effect of decompose hydroperoxide can be expected.As the commercially available product of sulphur system antioxidant and phosphorous antioxidant, the such as commercially available product such as ADKSTABTPP ((strain) ADEKA system, trade name), MARKAO-412S ((strain) ADEKA system, trade name), SUMILIZERTPS (Sumitomo Chemical (strain) system, trade name) can be enumerated.
In addition, in present embodiment, and with hindered phenol system antioxidant and sulphur system antioxidant, phosphorous antioxidant etc. as (C4) antioxidant, make resist shape good, to obtain in excellent solder heat resistance and resistance to solder flux corrosivity particularly preferably.
Solid constituent total amount in photosensitive polymer combination is set to 100 mass parts, and the content of (C4) antioxidant is preferably 0.2 ~ 15 mass parts.If be more than or equal to 0.2 mass parts, then exposure portion not easily stripping in development, if be less than or equal to 15 mass parts, then thermotolerance not easily reduces.In addition, from the same reason, the content of (C4) antioxidant is more preferably 0.2 ~ 10 mass parts, more preferably 0.5 ~ 5 mass parts, is particularly preferably 0.5 ~ 3 mass parts.
((C5) sulfur-bearing alcohol-based compounds)
(C5) composition is sulfur-bearing alcohol-based compounds, thinks that this sulfur-bearing alcohol-based compounds effectively plays a role as hydrogen donor, has the luminous sensitivity that more improves photosensitive polymer combination and the effect through day stability.
As (C5) sulfur-bearing alcohol-based compounds, such as mercaptobenzoxazole can be enumerated, mercaptobenzothiazoler, mercaptobenzimidazole, ethyl mercaptan, benzenethiol, mercapto-phenol, sulfydryl toluene, 2-mercaptoethyl amine, mercaptoethyl alcohol, sulfydryl dimethylbenzene, sulfo-xylenols, 2-mercaptoquinoline, mercaptoacetic acid, alpha-mercapto propionic acid, 3-mercaptopropionic acid, mercapto succinic acid, thiosalicylic acid, sulfydryl cyclohexane, alpha-mercapto diphenyl methane, C-mercapto-tetrazole, mercaptonaphthalene, sulfydryl naphthols, 4-sulfydryl biphenyl, sulfydryl hypoxanthine, mercaptopyridine, 2-mercaptopyrimidine, purinethol, sulfo-coumarone (チ オ Network マ ゾ Application), sulfo-coumothiazone (チ オ Network モ チ ア ゾ Application), butane-2, 3-bis-mercaptan, trithiocyanuric acid, 2, 4, 6-tri-thiol-s-triazine, 2-dibutylamino-4, 6-dimercapto-s-triazine, 2-anilino--4, 6-dimercapto-s-triazine etc.
These (C5) sulfur-bearing alcohol-based compounds can be used alone or in combination of two or more.In these, effectively play a role from as hydrogen donor, can more improve photosensitive polymer combination sensitivity and through day stability viewpoint set out, be preferably mercaptobenzoxazole, mercaptobenzothiazoler and mercaptobenzimidazole, be more preferably mercaptobenzimidazole.
About the content of (C5) sulfur-bearing alcohol-based compounds in photosensitive polymer combination, from the view point of the photosensitive polymer combination obtaining the pattern that can form excellent in resolution, with the solid constituent total amount of photosensitive polymer combination for benchmark, be preferably 0.01 ~ 5 mass parts, be more preferably 0.1 ~ 3 mass parts, more preferably 0.2 ~ 1.5 mass parts.If (C5) content of sulfur-bearing alcohol-based compounds is more than or equal to 0.01 mass parts, then the tendency of the solution having a photosensitive polymer combination not easily gelation, if be less than or equal to 5 mass parts, then can suppress the reduction of sensitivity.
< (D) photopolymerizable compound >
The photosensitive polymer combination of present embodiment contains photopolymerizable compound as (D) composition.
(D) as long as the compound that photopolymerizable compound has the functional group of display light polymerism is just not particularly limited; preferably enumerate the compound such as with oxirane unsaturated groups such as vinyl, allyl, propinyl, butenyl group, ethinyl, phenylene-ethynylene, dimaleoyl imino, Na Dike imide, (methyl) acryloyl groups; from reactive viewpoint, be more preferably the compound with (methyl) acryloyl group.
As (D) photopolymerizable compound, preferably enumerate such as (methyl) hydroxyalkyl acrylates class such as (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 2-hydroxy propyl ester; The list of the glycol such as ethylene glycol, methoxyl TEG, polyglycol or two (methyl) esters of acrylic acid; (methyl) acrylic amides such as N, N-dimethyl (methyl) acrylamide, N-methylol (methyl) acrylamide; (methyl) acrylate classes such as N, N-dimethyl aminoethyl (methyl) acrylate; Polynary (methyl) esters of acrylic acid of the polyvalent alcohols such as hexanediol, trimethylolpropane, pentaerythrite, double trimethylolpropane, dipentaerythritol, three-hydroxyethyl isocyanuric acid ester or their oxirane or propylene oxide adduct; The oxirane of phenols or (methyl) esters of acrylic acids of propylene oxide adduct such as polyethoxy two (methyl) acrylate of (methyl) acrylate, bis-phenol Α; (methyl) esters of acrylic acid of the glycidol ethers such as glycerin diglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, triglycidyl group isocyanuric acid ester; Melamine (methyl) acrylate etc.These (D) photopolymerizable compound can be used alone or in combination of two or more.
Solid constituent total amount in photosensitive polymer combination is set to 100 mass parts, (D) content of photopolymerizable compound is preferably 0.1 ~ 30 mass parts, be more preferably 1 ~ 20 mass parts, more preferably 1 ~ 15 mass parts, be particularly preferably 1.5 ~ 10 mass parts.If be more than or equal to 0.1 mass parts, then exposure portion not easily stripping in development, the tendency having the sensitivity of photosensitive polymer combination and resolution to improve, if be less than or equal to 30 mass parts, then has the tendency that thermotolerance improves.
< (E) inorganic filler >
The photosensitive polymer combination of present embodiment preferably contains inorganic filler as (E) composition.
(E) inorganic filler is the various characteristic such as adaptation, thermotolerance, hardness of film in order to improve photosensitive polymer combination and preferably uses.As (E) inorganic filler, preferably enumerate such as silicon dioxide (SiO 2), aluminium oxide (Al 2o 3), titanium dioxide (TiO 2), tantalum oxide (Ta 2o 5), zirconia (ZrO 2), silicon nitride (Si 3n 4), barium titanate (BaOTiO 2), barium carbonate (BaCO 3), magnesium carbonate, aluminium hydroxide, magnesium hydroxide, lead titanates (PbOTiO 2), lead zirconate titanate (PZT), zirconium lanthanium titanate lead (PLZT), gallium oxide (Ga 2o 3), spinel (MgOAl 2o 3), mullite (3Al 2o 32SiO 2), trichroite (2MgO2Al 2o 35SiO 2), talcum (3MgO4SiO 2h 2o), aluminium titanates (TiO 2al 2o 3), containing the zirconia (Y of yttria 2o 3zrO 2), barium silicate (BaO8SiO 2), boron nitride (BN), calcium carbonate (CaCO 3), barium sulphate (BaSO 4), calcium sulphate (CaSO 4), zinc paste (ZnO), magnesium titanate (MgOTiO 2), hydrotalcite, mica, burn till porcelain earth, carbon etc.These (E) inorganic fillers can be used alone or in combination of two or more.
About (E) inorganic filler, its maximum particle diameter is preferably 0.1 ~ 20 μm, is more preferably 0.1 ~ 10 μm, more preferably 0.1 ~ 5 μm, is particularly preferably 0.1 ~ 1 μm.If maximum particle diameter is less than or equal to 20 μm, then can suppress the reduction of electrical insulating property.Here, the maximum particle diameter of (E) inorganic filler utilizes laser diffractometry (according to JISZ8825-1 (calendar year 2001)) to measure.
(E) in inorganic filler, from the viewpoint of improving thermotolerance, be preferably silicon dioxide, from the viewpoint of the bonding strength that can improve the rear underfill material of solder heat resistance, resistance to anti-thread breakage (resistance to sudden heating) and resistance to PCT test and cured film, preferably barium sulfate.In addition, from the viewpoint of improving agglomeration preventing effect, above-mentioned barium sulphate preferably utilize be selected from aluminium oxide and organosilane based compound more than one carried out surface treatment.
Utilize more than one the element compositions having carried out the aluminium on surface-treated barium sulphate surface be selected from aluminium oxide and organosilane based compound to be preferably 0.5 ~ 10 atom %, be more preferably 1 ~ 5 atom %, more preferably 1.5 ~ 3.5 atom %.The element composition of the silicon on barium sulphate surface is preferably 0.5 ~ 10 atom %, is more preferably 1 ~ 5 atom %, more preferably 1.5 ~ 3.5 atom %.In addition, the element composition of the carbon on barium sulphate surface is preferably 10 ~ 30 atom %, is more preferably 15 ~ 25 atom %, more preferably 18 ~ 23 atom %.These elements composition can use XPS to measure.
As utilize be selected from aluminium oxide and organosilane based compound more than one carried out surface-treated barium sulphate, such as business can buy NanoFineBFN40DC (Japanese Solvay (strain) system, trade name).
When containing (E) inorganic filler, solid constituent total amount in photosensitive polymer combination is set to 100 mass parts, (E) content of inorganic filler is preferably 15 ~ 80 mass parts, be more preferably 15 ~ 70 mass parts, more preferably 20 ~ 70 mass parts, be particularly preferably 20 ~ 50 mass parts, be extremely preferably 20 ~ 45 mass parts.(E), when the content of inorganic filler is in above-mentioned scope, the film strength, thermotolerance, insulating reliability, resistance to sudden heating, resolution etc. of photosensitive polymer combination can more be improved.
In addition, when using barium sulphate as (E) inorganic filler, solid constituent total amount in photosensitive polymer combination is set to 100 mass parts, the content of barium sulphate is preferably 5 ~ 60 mass parts, be more preferably 10 ~ 50 mass parts, more preferably 10 ~ 40 mass parts, are particularly preferably 10 ~ 35 mass parts.When the content of barium sulphate is in above-mentioned scope, more can improve the bonding strength of solder heat resistance and the rear underfill material of resistance to PCT (PressureCookerTest) test and cured film.
< (F) pigment >
The photosensitive polymer combination of present embodiment preferably contains pigment as (F) composition.
(F) pigment is the material preferably used according to the color expected when hiding Wiring pattern etc.As (F) pigment, as long as suitably select the colorant showing desired color to use, as colorant, preferably enumerate the such as known colorant such as phthalocyanine blue, phthalocyanine green, iodine is green, diazonium is yellow, crystal violet.
When containing (F) pigment, the solid constituent total amount in photosensitive polymer combination is set to 100 mass parts, and the content of (F) pigment is preferably 0.1 ~ 5 mass parts, is more preferably 0.1 ~ 3 mass parts.(F) when the content of pigment is in above-mentioned scope, preferred from the viewpoint of hiding Wiring pattern.
Other compositions of < >
The photosensitive polymer combination of present embodiment can use the thinning agent for adjusting viscosity as required.As thinning agent, preferably enumerate such as organic solvent, photopolymerization monomer etc.Organic solvent such as can from as above-mentioned epoxy resin (a) with containing the reaction of vinyl monocarboxylic acid (b) suitable choice for use in solvent illustrated in spendable organic solvent.In addition, as photopolymerization monomer, preferably enumerate the material illustrated in above-mentioned (D) photopolymerizable compound.
The use amount of thinning agent preferably makes the solid constituent total amount in photosensitive polymer combination be the amount of 50 ~ 90 quality %, be more preferably and make the solid constituent total amount in photosensitive polymer combination be the amount of 60 ~ 80 quality %, more preferably make the solid constituent total amount in photosensitive polymer combination be the amount of 65 ~ 75 quality %.That is, amount of diluent during use thinning agent in photosensitive polymer combination is preferably 10 ~ 50 quality %, is more preferably 20 ~ 40 quality %, more preferably 25 ~ 35 quality %.By the use amount of thinning agent is set to above-mentioned scope, the coating of photosensitive polymer combination improves, and can form the pattern of fine more.
The photosensitive polymer combination of present embodiment can comprise hardening agent.As hardening agent, preferably enumerate the compound that himself utilizes heat, ultraviolet etc. to be cured or with the composition of present embodiment in contain the carboxyl of vinyl epoxy resin as (A) sour modification of light-cured resin composition, compound that hydroxyl utilizes heat, ultraviolet etc. to be cured.By using hardening agent, the thermotolerance of final cured film, adaptation, chemical reagent resistance etc. can be improved.
As hardening agent, such as, as heat-curable compounds, preferably enumerate epoxy compound, melamine compound, carbamide compound, oxazoline compound etc.As epoxy compound, preferably enumerate the bisphenol-type epoxy resins such as such as bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-A epoxy resin, brominated bisphenol a type epoxy resin, bisphenol-s epoxy resin; Phenolic resin varnish type epoxy resin; Biphenyl type epoxy resin; The hetero ring type epoxy resin such as triglycidyl isocyanurate; Di-toluene phenol-type epoxy resin etc.As melamine compound, preferably enumerate such as triamido triazine, hexa methoxy melamine, six butoxylated melamines etc.As carbamide compound, preferably enumerate dimethylolurea etc.
As hardening agent, from the viewpoint of the thermotolerance that more can improve cured film, preferably comprise be selected from epoxy compound (epoxy resin) and blocked isocyanate more than one, more preferably and with epoxy compound and blocked isocyanate.
As blocked isocyanate, use the addition reaction product of polyisocyanate compounds and isocyanate-terminated dose.As this polyisocyanate compounds, preferably enumerate polyisocyanate compounds and their adduct, biuret thing and the isocyanuric acid ester things etc. such as such as toluene diisocyanate, xylylene diisocyanate, phenylene vulcabond, naphthalene diisocyanate, two (isocyanatomethyl) cyclohexane, tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethyl hexamethylene diisocyanate, isophorone diisocyanate.
As isocyanate-terminated dose, preferably enumerate the phenol system end-capping reagents such as such as phenol, cresols, xylenols, chlorophenol and ethyl-phenol; The lactams system end-capping reagents such as epsilon-caprolactams, δ-valerolactam, butyrolactam and azetidinone; Ethyl acetoacetate and diacetone isoreactivity methylene base system end-capping reagent; The alcohol system end-capping reagents such as methyl alcohol, ethanol, propyl alcohol, butanols, amylalcohol, glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, benzylic ether, methyl glycollate, butyl glycolate, diacetone alcohol, methyl lactate and ethyl lactate; The oxime system end-capping reagents such as formaldoxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, diacetyl monoxime, cyclohexane oxime; The mercaptan system end-capping reagents such as butanethiol, hexyl mercaptans, tert-butyl mercaptan, benzenethiol, methylbenzene phenyl-sulfhydrate, ethyl thiophenol; The acid amides such as amide, benzamide system end-capping reagent; The imide series such as succinimide and maleimide end-capping reagent; The amine system end-capping reagents such as xylidin, aniline, butylamine, dibutylamine; The imidazoles system end-capping reagents such as imidazoles, 2-ethyl imidazol(e); The imines system end-capping reagents etc. such as methylene imine and propylidene imines.
Hardening agent is used alone a kind or combinationally use two or more.When using hardening agent, its content is preferably 2 ~ 50 mass parts relative to solid constituent total amount 100 mass parts in photosensitive polymer combination, is more preferably 2 ~ 40 mass parts, more preferably 3 ~ 30 mass parts, is particularly preferably 5 ~ 20 mass parts.By making the content of hardening agent be in above-mentioned scope, good developability can be maintained, and more improve the thermotolerance of the cured film formed.
In the photosensitive polymer combination of present embodiment, in order to improve the various characteristic such as thermotolerance, adaptation, chemical reagent resistance of final cured film further, can and use epoxy curing agent.
As the object lesson of such epoxy curing agent, preferably enumerate the imidazoles such as such as glyoxal ethyline, 2-ethyl-4-methylimidazole, 1 benzyl 2 methyl imidazole, 2-phenylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole; The guanidine such as acetylguanamine, benzoguanamine amine; The polyamine classes such as diaminodiphenyl-methane, m-phenylenediamine, m-xylene diamine, diamino diphenyl sulfone, dicyandiamide, urea, urea derivative, melamine, polynary hydrazides; Be selected from least one in their acylate and epoxy adduct; The amine complex of boron trifluoride; The pyrrolotriazine derivatives classes such as ethyl diamido-S-triazine, 2,4-diamido-S-triazines, 2,4-diamido-6-xylyl-S-triazines; The tertiary amines such as Trimethylamine, N, N-dimethyl octyl amine, N-benzyl dimethyl amine, pyridine, N-methylmorpholine, six (N-methyl) melamine, 2,4,6-tri-(Dimethylaminophenol), tetramethyl guanidine, m-aminophenol; The Polyphenols such as polyvinylphenol, polyvinylphenol bromide, phenol novolacs, alkylphenol novolaks; The organic phosphine classes such as tributylphosphine, triphenylphosphine, three-2-cyano ethyl phosphines; Three-normal-butyl (phosphonium salt class such as 2,5-dihydroxy phenyl) phosphonium bromide, six decyl tributyl phosphonium chlorides; The quaternary ammonium salts such as benzyltrimethylammonium chloride, phenyl tributyl ammonium chloride; Above-mentioned multi-anhydride; Diphenyl iodine tetrafluoroborate, triphenyl sulphur hexafluoro antimonate, 2,4,6-triphenyl thio-pyrylium hexafluorophosphates etc.
Epoxy curing agent is used alone a kind or combinationally use two or more, is preferably 0.01 ~ 20 quality %, is more preferably 0.1 ~ 10 quality % in photosensitive polymer combination.
The photosensitive polymer combination of present embodiment, can use the polymerization inhibitors such as quinhydrones, methylnaphthohydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol as required; The tackifier such as bentonite, polynite; The defoamers such as silicon-type, fluorine system, vinylite system; The known usual various adjuvants such as silane coupling agent.
Further, the fire retardant such as phosphate compound, aromatic condensation phosphate, Halogen condensed phosphoric acid esters of brominated epoxy compound, sour modification brominated epoxy compound, antimonial, phosphorus series compound can be used.
(elastic body)
The photosensitive polymer combination of present embodiment can contain elastic body.Elastic body is especially preferably using the photosensitive polymer combination of present embodiment for the manufacture of during conductor package substrate.By adding elastic body in the photosensitive polymer combination of present embodiment, and utilize ultraviolet, heat etc. to be cured reaction, can suppress to result from by (A) sour modification containing vinyl epoxy resin cure shrinkage caused by resin internal strain (internal stress), pliability and cementability reduce.
As elastic body, preferably enumerate styrene series elastomer, ethylene series elastic body, carbamate based elastomers, polyester-based elastomer, polyamide-based elastic body, acrylic elastomer and silicon-type elastic body etc.These elastic bodys are made up of hard segment components and soft segment components, and it has been generally acknowledged that the former contributes to thermotolerance and intensity, the latter contributes to flexibility and obdurability.
In addition, except above-mentioned elastic body, rubber-modified epoxy resin can also be used.Rubber-modified epoxy resin, such as, carry out modification by use two terminal carboxylic modified version butadiene-propylene nitrile rubber, terminal amino group modified organic silicon rubber etc. to part or all epoxy radicals of above-mentioned bisphenol f type epoxy resin, bisphenol A type epoxy resin, tris-phenol type epoxy resin, phenol novolak type epoxy resin or cresol novolak type epoxy resin and obtain.In these elastic bodys, from the viewpoint of shear bond, preferably enumerate two terminal carboxyl group modified butadiene-acrylonitrile copolymers, as the ESPEL (Hitachi changes into (strain) system, ESPEL1612,1620 (trade names)) of polyester-based elastomer with hydroxyl.
Elastomeric use level is preferably 2 ~ 30 mass parts relative to (A) sour modification containing vinyl epoxy resin 100 mass parts, is more preferably 4 ~ 20 mass parts, more preferably 10 ~ 20 mass parts.If be more than or equal to 2 mass parts, then there is cured film in the tendency of the elastic modulus step-down of high-temperature area, if be less than or equal to 30 mass parts, then have the tendency of unexposed portion stripping in developer solution.
The photosensitive polymer combination of present embodiment can by using roller mill, ball mill etc. will headed by above-mentioned (A) ~ (F) composition, mixing according to the various uniform composition expecting to use, be obtained by mixing.
In addition, the photosensitive polymer combination of present embodiment is preferably liquid.Liquid by being formed, can easily form permanent mask resist by various coating process described later.
[photosensitive element, permanent mask resist and printing distributing board]
The photosensitive polymer combination of present embodiment is suitably used for forming photosensitive element and permanent mask resist, and the photosensitive element of present embodiment and permanent mask resist use the photosensitive polymer combination of present embodiment to be formed.
The photographic layer that the photosensitive element of present embodiment has supporter and uses the photosensitive polymer combination of present embodiment to be formed on this supporter.As supporter, preferably enumerate the resin molding that the polyolefin resin films etc. such as the polyester resin films such as such as polyethylene terephthalate, tygon, polypropylene have thermotolerance and solvent resistance, from the position of the transparency, preferably use polyethylene terephthalate film.In addition, if consider to obtain physical strength, good resolution etc., then the thickness of supporter is preferably 1 ~ 100 μm, is more preferably 1 ~ 50 μm, more preferably 1 ~ 30 μm.
The photosensitive element of present embodiment such as can obtain as follows: utilize the methods such as infusion process, spray-on process, stick coating method, rolling method, spin-coating method coated on above-mentioned supporter with the thickness (after drying: 10 ~ 200 μm) meeting purposes and form film by the photosensitive polymer combination of present embodiment, with 70 ~ 150 DEG C of dryings, 5 ~ 30 minutes degree, form photographic layer.
Permanent mask resist and the printing distributing board with this permanent mask resist of present embodiment, such as, carry out image formation as follows.First, utilize silk screen print method, spray-on process, rolling method, curtain to be coated with the method such as method, electrostatic applications method and the photosensitive polymer combination of present embodiment is coated on the base material of resist to be formed (such as with the thickness (after drying: 10 ~ 200 μm) meeting purposes, the copper-clad laminated board etc. of printing distributing board) above form film, with 60 ~ 110 DEG C of these films of drying.In addition, this film can also be replaced and by the photographic layer transfer printing (lamination) of photosensitive element on the base material of this resist to be formed.In this case, use normal pressure laminating machine or vacuum laminator as required, the dry film on supporter is pasted onto on base material.
After base material is formed photographic layer (film), it is made directly to contact with negative film, or across transparent film, to be preferably 10 ~ 1,000mJ/cm 2energy exposure ultraviolet isoreactivity light, peeling off this resin molding when having pasted resin molding, using dilute alkaline aqueous solution that removing (development) is dissolved in unexposed portion.
Then, exposed portion is fully solidified by post-exposure (ultraviolet exposure), rear heating or post-exposure and rear heating and obtains cured film.Post-exposure preference is as 1 ~ 5J/cm 2, rear heating preferably 100 ~ 200 DEG C, 30 minutes ~ 12 hours.
The permanent mask resist obtained thus, not easily there is the undercutting that bottom is cut off, not easily there is the disappearance on resist top, the live width in the pars intermedia (central part) of patterned section and most deep (bottom) is not more than the live width of surface element, and the rectilinearity therefore with pattern contour is good and resist shape is excellent, the pattern of excellent in resolution.In addition, this permanent mask resist has the pattern separating the formation excellent in stability of spacing between the pore size through miniaturization of adjoint electronics miniaturization and high performance in recent years and hole.
Embodiment
, illustrate the present invention further according to embodiment below, but the present invention is not by any restriction of these embodiments.
(evaluation method)
(1) evaluation of surface cure
Utilize applicator to be that the photosensitive polymer combination of each embodiment and comparative example is coated in the PET film of thickness 35 μm by the mode of 35 μm with dried thickness, form film.Then, hot air circulation type drying machine is used, with 80 DEG C of dryings 20 minutes.The infrared absorption spectrum (ATR (AttenuatedTotalReflection: attenuated total reflection) method) of the film coated surface obtained is measured with following condition.
Determinator: ThermoFisherScientific (strain) system, trade name: NicoletiS50R
Cumulative frequency: 128 times
Then, use ultraviolet exposure apparatus according ((strain) HITECH system, trade name: HTE-5102S) with 600mJ/cm 2exposure expose.Measure the infrared absorption spectrum (ATR method) of the rear film coated surface of exposure with condition similar to the above, obtained before and after exposure at 1470cm by following formula -1the rate of change of carbon-to-carbon double bond occurred, using the mean value of cumulative frequency 3 times as surface cure (%).
Rate of change (the %)=100-(carbon-to-carbon double bond amount × 100 before the carbon-to-carbon double bond amount/exposure after exposure) of double bond
(2) evaluation of luminous sensitivity
Utilize applicator to be that the photosensitive polymer combination of each embodiment and comparative example is coated in the PET film of thickness 35 μm by the mode of 35 μm with dried thickness, form film.Then, hot air circulation type drying machine is used, with 80 DEG C of dryings 20 minutes.Then, stage metraster 41 sections (Hitachi changes into (strain) makes) is made to be sealed at film, with 50mJ/cm 2the ultraviolet (large Japanese SCREEN manufactures (strain) direct imaging machine processed, " LI9200 (model) ") of comprehensive irradiation predetermined cumulative exposure amount.Then, after developing 60 seconds with the aqueous sodium carbonate of 1 quality %, confirm not develop and the hop count of residual film.According to hop count, evaluate according to following benchmark.
A (excellent): be more than or equal to 10 sections
B (good): 6 ~ 9 sections
C (bad): be less than or equal to 5 sections
(3) evaluation of bottom curability
Utilize applicator to be that the photosensitive polymer combination of each embodiment and comparative example is coated in the PET film of thickness 35 μm by the mode of 35 μm with dried thickness, form film.Then, hot air circulation type drying machine is used, with 80 DEG C of dryings 20 minutes.The infrared absorption spectrum (ATR method) of the film coated surface obtained is measured with following condition.
Determinator: ThermoFisherScientific (strain) system, trade name: NicoletiS50R
Cumulative frequency: 128 times
Then, use ultraviolet exposure apparatus according ((strain) HITECH system, trade name: HTE-5102S) with 600mJ/cm 2exposure expose.Then, peel the film through exposure off from PET film, measure the infrared absorption spectrum (ATR method) of the film of the rear side, PET film face of exposure with condition similar to the above.Obtained before and after exposure at 1470cm by following formula -1the rate of change of carbon-to-carbon double bond occurred, using the mean value of cumulative frequency 3 times as curability (%) bottom film.
Rate of change (the %)=100-(carbon-to-carbon double bond amount × 100 before the carbon-to-carbon double bond amount/exposure after exposure) of double bond
(4) evaluation of resist shape
Silk screen print method is utilized to be that the photosensitive polymer combination of each embodiment and comparative example is coated 50cm × 50cm size and on the copper-clad laminated substrate of thickness 0.6mm (Hitachi changes into (strain) system, trade name: MCL-E-67) by the mode of 35 μm with dried thickness, after forming film, use hot air circulation type drying machine with 80 DEG C of dryings 20 minutes.
Then, make to have the pore size shown in Fig. 2 and be 100 μm and the spacing that separates between hole is that the pattern of 100 μm and pore size are 80 μm and the spacing that separates between hole is that the negative mask of the pattern of 80 μm is closely sealed with film respectively, use ultraviolet exposure apparatus according ((strain) HITECH system, trade name: HTE-5102S) to expose with the predetermined degree of exposure shown in table 1 ~ 6.
Afterwards, use the aqueous sodium carbonate of 1 quality % with 0.18MPa (1.8kgf/cm 2) press atomization developed for 60 seconds, to unexposed portion carry out dissolving development.Then, use ultraviolet exposure apparatus according ((strain) GSYUASALighting system, trade name: conveyor-type UV irradiation unit) with 1000mJ/cm 2exposure expose after, with 150 DEG C heating 1 hour, make test film.
With epoxy resin ((Mitsubishi Chemical's (strain) system, EPIKOTE828 (trade name)) with use triethylene tetramine to carry out note type as the thermoset resin of hardening agent to the figuratum test film of formation and after fully solidifying, muller (REFINETEC (strain) system, trade name: RefinePolisher) is utilized to grind, cut out the cross section of pattern, utilize metal microstructure sem observation resist shape, evaluate according to following benchmark.Fig. 1 schematically illustrates the cross sectional shape of resist.
A (excellent): resist shape is rectangular or trapezoidal, and the rectilinearity of pattern contour is good.
B (bad): resist shape confirms undercutting, hangover or thicker, or the rectilinearity of pattern contour is poor.
(5) evaluation of aperture precision
Silk screen print method is utilized to be that the photosensitive polymer combination of each embodiment and comparative example is coated 50cm × 50cm size and on the copper-clad laminated substrate of thickness 0.6mm (Hitachi changes into (strain) system, trade name: MCL-E-67) by the mode of 35 μm with dried thickness, after forming film, use hot air circulation type drying machine with 80 DEG C of dryings 20 minutes.
Then, the negative mask making to have pattern shown in Fig. 2 is closely sealed with film respectively, uses ultraviolet exposure apparatus according ((strain) HITECH system, trade name: HTE-5102S) with 600mJ/cm 2exposure expose.Afterwards, use the aqueous sodium carbonate of 1 quality % with 0.18MPa (1.8kgf/cm 2) press atomization developed for 60 seconds, to unexposed portion carry out dissolving development, thus make test film.For the test film pattern obtained, evaluate according to following benchmark.
A (excellent): 100 μm and the pattern reproduction of 80 μm 80%.
B (bad): 100 μm and the pattern of 80 μm only reproduced less than 80%.
Here, use microscope, be amplified to 700 times, observe the pattern of 100 μm and 80 μm, when 100 μm of patterns, the situation defining bottom portion is designated as pattern is reproduced with the size being more than or equal to 80 μm (being more than or equal to 80% relative to pattern diameter).When 80 μm of patterns, the situation defining bottom portion is designated as pattern is reproduced with the size being more than or equal to 64 μm.In addition, in the judgement of " A ", " B ", by the total number of patterns of formation relative to 100 μm and the total number of patterns of the 80 μm average evaluation that is more than or equal to 80% be " A ".
(6) evaluation (i) of solder heat resistance
Water soluble flux (ALPHAMETAL (strain) system, trade name: K-183) is coated with on the test film made with test film the same terms of using in the evaluation of above-mentioned (4) resist shape, after being set as flooding for 10 seconds in the solder bath of 265 DEG C, take out from solder layer.With dipping and taking-up be 1 circulation, repeatedly 6 circulate after, visualization appearance of film, evaluates according to following benchmark.
A (excellent): in the scope of film 30cm × 30cm, unconfirmed to cosmetic variation.
B (good): in the scope of film 30cm × 30cm, confirms floating or heaving of 1 ~ 5 films.
C (bad): in the scope of film 30cm × 30cm, confirms and is more than or equal to floating or heaving of 6 films.
(7) evaluation (ii) of solder heat resistance
Leave solder flux (thousand live metal industry (strain) system, trade name: RMASR-209) is coated with on the test film made with test film the same terms of using in the evaluation of above-mentioned (4) resist shape, after being set as flooding for 10 seconds in the solder bath of 280 DEG C, take out from solder layer.Be 1 circulation with this dipping and taking-up, repeatedly after 10 circulations, the appearance of film of the test film that visualization is taken out, evaluates according to following benchmark.
A: the cosmetic variation to resist film unconfirmed.
B: the stripping confirming a small amount of resist film, but the degree being practical upper no problem.
C: confirm heaving or peeling off of resist film.
(8) resistance to anti-thread breakage evaluation
After keeping 30 minutes with the test film made with test film the same terms of using in the evaluation of above-mentioned (4) resist shape at-65 DEG C, keep 30 minutes at 150 DEG C, using above operation as 1 circulation, after repeating 1000 circulations, the appearance of film of visualization test film, evaluates according to following benchmark.
A (excellent): in the scope of film 30cm × 30cm, unconfirmed to cosmetic variation.
B (good): in the scope of film 30cm × 30cm, confirms floating or heaving of 1 ~ 5 films.
C (bad): in the scope of film 30cm × 30cm, confirms and is more than or equal to floating or heaving of 6 films.
(9) evaluation of adaptation
Silk screen print method is utilized to be that the photosensitive polymer combination of each embodiment and comparative example is coated copper-clad laminated substrate (Hitachi changes into (strain) system of copper surface having been carried out to the thickness 0.6mm of polishing grinding (on depth direction alligatoring 5 μm) by the mode of 35 μm with dried thickness, trade name: MCL-E-67) and copper surface has been carried out to copper-clad laminated substrate (Hitachi changes into (strain) system of thickness 0.6mm of chemical grinding (using MEC (strain) the lapping compound CZ8101 alligatoring 0.5 μm in the depth direction of making), trade name: MCL-E-67) on, after forming film, use hot air circulation type drying machine with 80 DEG C of dryings 20 minutes.
Then, the negative mask making to have pattern shown in Fig. 2 is closely sealed with film respectively, uses ultraviolet exposure apparatus according ((strain) HITECH system, trade name: HTE-5102S) with 600mJ/cm 2exposure expose.Afterwards, use the aqueous sodium carbonate of 1 quality % with 0.18MPa (1.8kgf/cm 2) press atomization developed for 60 seconds, to unexposed portion carry out dissolving development.Then, use ultraviolet exposure apparatus according ((strain) GSYUASALighting system, trade name: conveyor-type UV irradiation unit) with 1000mJ/cm 2exposure expose, with 150 DEG C heating 1 hour, make test film.
For the test film obtained, according to JISK5600, make the gridiron pattern of 100 1mm, after pasting cellophane adhesive tape (meter Qi Bang (strain) system, trade name: Cellotape (registered trademark)), carry out the disbonded test of forcing to peel off cellophane adhesive tape in the direction of 90 degree.Observe tessellated stripping state, evaluate according to following benchmark.
A (excellent): be more than or equal to 90/100 unstripped.
B (good): be more than or equal to 50/100 and be less than 90/100 unstripped.
C (bad): be more than or equal to 0/100 and be less than 50/100 unstripped.
(10) solvent resistance
By with the test film made with test film the same terms of using in the evaluation of above-mentioned (4) resist shape in isopropyl alcohol with room temperature immersion 30 minutes, range estimation confirms that outward appearance has without exception.Then, after the film of test film after impregnating being pasted cellophane adhesive tape (meter Qi Bang (strain) system, trade name: Cellotape (registered trademark)), carry out the disbonded test of forcing to peel off cellophane adhesive tape in the direction of 90 degree, range estimation confirms that film is with or without stripping, evaluates according to following benchmark.
A (excellent): unconfirmed have exception to appearance of film, and unstripped.
B (bad): confirming appearance of film has exception, or there occurs stripping.
(11) acid resistance
By with the test film made with test film the same terms of using in the evaluation of above-mentioned (4) resist shape in 10 quality % aqueous hydrochloric acid solutions with room temperature immersion 30 minutes, range estimation confirms that outward appearance has without exception.Then, after the film of test film after impregnating being pasted cellophane adhesive tape (meter Qi Bang (strain) system, trade name: Cellotape (registered trademark)), carry out the disbonded test of forcing to peel off cellophane adhesive tape in the direction of 90 degree, range estimation confirms that film is with or without stripping, evaluates according to following benchmark.
A (excellent): unconfirmed have exception to appearance of film, and unstripped.
B (bad): confirming appearance of film has exception, or there occurs stripping.
(12) alkali resistance
By with the test film made with test film the same terms of using in the evaluation of above-mentioned (4) resist shape in 5 quality % sodium hydrate aqueous solutions with room temperature immersion 30 minutes, range estimation confirms that outward appearance has without exception.Then, after the film of test film after impregnating being pasted cellophane adhesive tape (meter Qi Bang (strain) system, trade name: Cellotape (registered trademark)), carry out the disbonded test of forcing to peel off cellophane adhesive tape in the direction of 90 degree, range estimation confirms that film is with or without stripping, evaluates according to following benchmark.
A (excellent): unconfirmed have exception to appearance of film, and unstripped.
B (bad): confirming appearance of film has exception, or there occurs stripping.
(13) the corrosive evaluation of resistance to solder flux
In the evaluation of above-mentioned (4) resist shape, make the pattern shown in Fig. 2 for the square lattice-shaped pattern of the 1mm shown in Fig. 3, in addition, operate in the same manner as the evaluation of above-mentioned (4) resist shape, obtain test film.Then, whole of the test film of gained is coated with highly active water soluble flux (ALPHAMETAL (strain) system, trade name: K-183), places 3 minutes in the perpendicular mode of putting, remove unnecessary solder flux.Then, by test film 130 DEG C of preheatings 1 minute, then flood after 20 seconds in the solder bath of 280 DEG C, take out from solder bath.Place cooling in room temperature to wash after 1 minute, after wiping water droplet, visual observations outward appearance.The wide cellophane adhesive tape of 24mm (meter Qi Bang (strain) system, trade name: Cellotape (registered trademark)) is pasted in addition at the minimum circuit width place of test film, carry out the disbonded test of forcing to peel off cellophane adhesive tape in the direction of 90 degree, test film outward appearance after visual observations stripping, evaluates according to following benchmark.
5: even if the also stripping to there is Resist portions completely unconfirmed after disbonded test.
4: after disbonded test, confirm exist Resist portions less than 20% stripping.
3: confirms a small amount of albefaction in there is Resist portions before disbonded test, confirm after disbonded test exist Resist portions less than 20% stripping, but practical upper no problem.
2: confirms albefaction in there is Resist portions before disbonded test, confirm after disbonded test exist Resist portions more than 20% stripping.
1: confirming significant albefaction in there is Resist portions before disbonded test, after disbonded test, confirming significant stripping.
(14) chemically-resistant plating
For with the test film made with test film the same terms of using in the evaluation of above-mentioned (4) resist shape, use electroless nickel bath and the chemical gilding bath of commercially available product, carry out plating with the condition of 5 μm, nickel, gold 0.05 μm of thickness.After plating, range estimation confirms the infiltration with or without plating.Then, after the film of test film after impregnating being pasted cellophane adhesive tape (meter Qi Bang (strain) system, trade name: Cellotape (registered trademark)), carry out the disbonded test of forcing to peel off cellophane adhesive tape in the direction of 90 degree, range estimation confirms that film is with or without stripping, evaluates according to following benchmark.
A: do not see infiltration and peel off.
B: see infiltration after plating, but do not see stripping.
C: see stripping after plating.
(synthesis example 1; Acid modification is containing the synthesis of vinyl epoxy resin (I))
By cresol novolak type epoxy resin, (Nippon Steel lives in aurification (strain) system, trade name: YDCN704, general formula (I), Y 1=glycidyl, R 11=methyl) 220 mass parts, acrylic acid 72 mass parts, quinhydrones 1.0 mass parts, carbitol acetate 180 mass parts mixing, be heated to 90 DEG C and stir, thus reaction mixture is dissolved.Then, be cooled to 60 DEG C, mixing benzyltrimethylammonium chloride 1 mass parts, is heated to 100 DEG C, make its react to solid constituent acid number be 1mgKOH/g.Then, mixing tetrabydrophthalic anhydride 152 mass parts and carbitol acetate 100 mass parts, be heated to 80 DEG C, stir 6 hours.After being cooled to room temperature, using carbitol acetate to dilute, make solid component concentration become 60 quality %, obtain comprising the solution of sour modification containing vinyl epoxy resin (I).
Be explained, the solid constituent acid number in embodiment is measured by neutralization titration.Specifically, acetone 30g is added containing in the solution 1g of vinyl epoxy resin to comprising sour modification, after further uniform dissolution, sour modification is comprised containing the phenolphthalein added as indicator appropriate in the solution of vinyl epoxy resin to above-mentioned, use the sodium hydrate aqueous solution of 0.1N to carry out titration, thus measure.
(synthesis example 2; Acid modification is containing the synthesis of vinyl epoxy resin (II)-a)
By bisphenol f type epoxy resin, (Nippon Steel lives in aurification (strain) system, trade name: YDF2001, general formula (II), Y 2=glycidyl, R 12=H) 475 mass parts, acrylic acid 72 mass parts, quinhydrones 0.5 mass parts, carbitol acetate 120 mass parts mixing, be heated to 90 DEG C and stir, thus reaction mixture is dissolved.Then, be cooled to 60 DEG C, mixing benzyltrimethylammonium chloride 2 mass parts, is heated to 100 DEG C, make its react to solid constituent acid number be 1mgKOH/g.Then, by tetrabydrophthalic anhydride 230 mass parts and the mixing of carbitol acetate 85 mass parts, be heated to 80 DEG C, stir 6 hours.After being cooled to room temperature, using carbitol acetate to dilute, make solid component concentration become 60 quality %, obtain comprising the solution of sour modification containing vinyl epoxy resin (II)-a.
(synthesis example 3; Acid modification is containing the synthesis of vinyl epoxy resin (IV)-a)
In the flask being provided with thermometer, tap funnel, cooling tube and stirring machine, add two (4-hydroxy phenyl) methane 272 mass parts of dissolving with 80 DEG C, start to stir at 80 DEG C.Add methane-sulforic acid 3 mass parts wherein, maintain the mode of 80 ~ 90 DEG C of scopes with liquid temperature, drip paraformaldehyde aqueous solution (concentration: 92 quality %) 16.3 mass parts with 1 hour.After dropping terminates, be heated to 110 DEG C, stir 2 hours.Then, add methylisobutylketone 1000 mass parts further, to move in separating funnel and to wash.Continuous washing is until after rinse water display neutrality, under heating decompression, (temperature: 220 DEG C, pressure: 66.7Pa) is from organic layer by solvent and unreacted two (4-hydroxy phenyl) methane removing, obtains bis-phenol system novolac resin 164 mass parts as brown solid.The softening point of the bis-phenol system novolac resin obtained is 74 DEG C, hydroxyl equivalent is 154g/eq.
Then, to being provided with the flask of thermometer, tap funnel, cooling tube and stirring machine while carry out nitrogen purge, bis-phenol system obtained above novolac resin 154 mass parts, chloropropylene oxide 463 mass parts, normal butyl alcohol 139 mass parts and tetraethyl benzyl ammonium chloride 2 mass parts are mixed and dissolve.Then, be heated to 65 DEG C, after being decompressed to the pressure of azeotropic, dripping sodium hydrate aqueous solution (concentration: 49 quality %) 90 mass parts with 5 hours with constant speed, stir 30 minutes., utilize the fraction seperation that Dean-Stark separation vessel (Dean-StarkTrap) will be distillated by azeotropic therebetween, removing water layer, is back to oil reservoir in flask (reaction system), while react.Then, in the thick epoxy resin unreacted chloropropylene oxide distillation removing obtained by decompression distillation (temperature: 22 DEG C, pressure: 1.87kPa), add methylisobutylketone 590 mass parts, normal butyl alcohol 177 mass parts dissolving.In this solution, add sodium hydrate aqueous solution (concentration: 10 quality %) 10 mass parts, after 2 hours, repeatedly wash three time with the water of 150 mass parts 80 DEG C of reactions, until the pH of cleaning fluid is neutral.Confirming the pH washing cleaning fluid used is for the third time neutrality.Then, azeotropic is utilized to dewater to (in reaction system) in flask, after carrying out secondary filter, under reduced pressure (pressure: 1.87kPa) is by solvent distillation removing, obtain as brown viscous liquid, bis-phenol system phenolic resin varnish type epoxy resin that the present invention is used (has Y in general formula (IV) 4=glycidyl, R 13the epoxy resin (a) of the structural unit of=H).The hydroxyl equivalent of this epoxy resin is 233g/eq.
In epoxy resin (a) 450 mass parts obtained above, mix acrylic acid 124 mass parts, quinhydrones 1.5 mass parts, carbitol acetate 250 mass parts, be heated to 90 DEG C and stir, reaction mixture is dissolved.Then, after being cooled to 60 DEG C, mixing benzyltrimethylammonium chloride 2 mass parts, is heated to 100 DEG C, make its react to acid number be 1mgKOH/g.Then, tetrabydrophthalic anhydride 230 mass parts and carbitol acetate 180 mass parts are mixed with above-mentioned reactant, is heated to 80 DEG C, react 6 hours.Then, be cooled to room temperature, use carbitol acetate to dilute, make solid component concentration become 60 quality %, obtain comprising the solution of sour modification containing vinyl epoxy resin (IV)-a.
Be explained, the softening point of resin carries out measuring (programming rate: 5 DEG C/min) according to the ball and ring method specified in JIS-K7234:1986.
(synthesis example 4; Acid modification is containing the synthesis of vinyl epoxy resin (IV)-b)
In the flask being provided with thermometer, tap funnel, cooling tube and stirring machine, add 2,2-two (4-hydroxy phenyl) propane 272 mass parts of dissolving with 80 DEG C, start to stir at 80 DEG C.Add methane-sulforic acid 3 mass parts wherein, maintain the mode of 80 ~ 90 DEG C of scopes with liquid temperature, drip paraformaldehyde (92 quality %) 16.3 mass parts with 1 hour.After dropping terminates, be heated to 110 DEG C, stir 2 hours.Then, add methylisobutylketone 1000 mass parts further, to move in separating funnel and to wash.Continuous washing is until after rinse water display neutrality, heating decompression under (temperature: 240 DEG C, pressure: 26.7Pa) from organic layer by solvent and unreacted 2,2-(4-hydroxy phenyl) propane removes, and obtains bis-phenol system novolac resin 164 mass parts as brown solid.The softening point of the bis-phenol system novolac resin obtained is 87 DEG C, hydroxyl equivalent is 174g/eq.
Then, to being provided with the flask of thermometer, tap funnel, cooling tube and stirring machine while carry out nitrogen purge, bis-phenol system obtained above novolac resin 154 mass parts, chloropropylene oxide 463 mass parts, normal butyl alcohol 139 mass parts and tetraethyl benzyl ammonium chloride 2 mass parts are mixed and dissolve.Then, be heated to 65 DEG C, after being decompressed to the pressure of azeotropic, dripping sodium hydrate aqueous solution (concentration: 49 quality %) 90 mass parts with 5 hours with constant speed, stir 30 minutes., utilize the fraction seperation that Dean-Stark separation vessel (Dean-StarkTrap) will be distillated by azeotropic therebetween, removing water layer, is back to oil reservoir in flask (reaction system), while react.Then, in the thick epoxy resin unreacted chloropropylene oxide distillation removing obtained by decompression distillation (temperature: 22 DEG C, pressure: 1.87kPa), add methylisobutylketone 590 mass parts, normal butyl alcohol 177 mass parts dissolving.In this solution, add sodium hydrate aqueous solution (concentration: 10 quality %) 10 mass parts, after 2 hours, repeatedly wash three time with the water of 150 mass parts 80 DEG C of reactions, until the pH of cleaning fluid is neutral.Confirming the pH washing cleaning fluid used is for the third time neutrality.Then, azeotropic is utilized to dewater to (in reaction system) in flask, after carrying out secondary filter, under reduced pressure (pressure: 1.87kPa) is by solvent distillation removing, obtain as brown viscous liquid, bis-phenol system phenolic resin varnish type epoxy resin that the present invention is used (has Y in general formula (IV) 4=glycidyl, R 13the epoxy resin (a) of the structural unit of=methyl).The hydroxyl equivalent of this epoxy resin is 233g/eq.
In epoxy resin (a) 450 mass parts obtained above, mix acrylic acid 124 mass parts, quinhydrones 1.5 mass parts, carbitol acetate 250 mass parts, be heated to 90 DEG C and stir, reaction mixture is dissolved.Then, be cooled to 60 DEG C, mixing benzyltrimethylammonium chloride 2 mass parts, is heated to 100 DEG C, make its react to acid number be 1mgKOH/g.Then, tetrabydrophthalic anhydride 230 mass parts and carbitol acetate 180 mass parts are mixed with above-mentioned reactant, is heated to 80 DEG C, react 6 hours.Then, be cooled to room temperature, use carbitol acetate to dilute, make solid component concentration become 60 quality %, obtain comprising the solution of sour modification containing vinyl epoxy resin (IV)-b.
(synthesis example 5; Acid modification is containing the synthesis of vinyl epoxy resin (IV)-c)
Mix in the flask being provided with thermometer, tap funnel, cooling tube and stirring machine bisphenol F phenolic type epoxy resin (in DIC (strain) system, trade name: EXA-7376, general formula (IV), Y 4and Y 5=glycidyl, R 13=hydrogen atom) 350 mass parts, acrylic acid 70 mass parts, methylnaphthohydroquinone 0.5 mass parts, carbitol acetate 120 mass parts, be heated to 90 DEG C and stir, thus reacting, potpourri is dissolved completely.Then, the solution obtained is cooled to 60 DEG C, adds triphenylphosphine 2 mass parts, be heated to 100 DEG C, make its acid number reacted to solution be 1mgKOH/g.In reacted solution, add tetrabydrophthalic anhydride (THPAC) 98 mass parts and carbitol acetate 85 mass parts, be heated to 80 DEG C, react 6 hours.Then, be cooled to room temperature, obtain solid component concentration be 73 quality % comprise sour modification containing the solution of vinyl epoxy resin (IV)-c.
(synthesis example 6; Acid modification is containing the synthesis of vinyl epoxy resin (II)-b)
Bisphenol f type epoxy resin (Mitsubishi Chemical's (strain) system, trade name: in 4004, epoxide equivalent: 526g/eq, general formula (II), Y is mixed in the flask being provided with thermometer, tap funnel, cooling tube and stirring machine 2=hydrogen atom, R 12=hydrogen atom) 1,052 mass parts, acrylic acid (b) 144 mass parts, methylnaphthohydroquinone 1 mass parts, carbitol acetate 850 mass parts and solvent naphtha 100 mass parts, heat with 70 DEG C and stir, being dissolved by potpourri.Then, solution is cooled to 50 DEG C, mixing triphenylphosphine 2 mass parts, solvent naphtha 75 mass parts, be heated to 100 DEG C, carry out reacting until solid constituent acid number is less than or equal to 1mgKOH/g.Then, the solution obtained is cooled to 50 DEG C, mixing tetrabydrophthalic anhydride (THPAC) 745 mass parts, carbitol acetate 75 mass parts and solvent naphtha 75 mass parts, be heated to 80 DEG C, react 6 hours.Then, be cooled to room temperature, obtain solid constituent acid number 80mgKOH/g, solid constituent is 62 quality % comprises the solution of sour modification containing vinyl epoxy resin (II)-b.
Embodiment 1 ~ 32 and comparative example 1 ~ 32
Cooperation composition according to table 1 ~ 6 carrys out complexing compositions, utilizes 3 roller mills to carry out mixing, modulation photosensitive polymer combination.Add carbitol acetate and become 70 quality % to make solid component concentration, obtain photosensitive polymer combination.Use the photosensitive polymer combination obtained, evaluate based on above-mentioned evaluation method.Evaluation result is shown in table 1 ~ 6.Be explained, in table, the unit of the use level of each composition is mass parts, and in table, the use level of (A) composition refers to the use level of the solution comprising the epoxy resin obtained by each synthesis example.
Embodiment 33,34 and comparative example 33,34
According to the cooperation composition shown in table 6, by method modulation photosensitive polymer combination similarly to Example 1.With each photosensitive polymer combination of methyl ethyl ketone dilution gained, coat after in PET film, 90 DEG C of dryings 10 minutes, form the photographic layer be made up of photosensitive polymer combination of thickness 25 μm.To fit thereon further polyethylene film (protective seam), make photosensitive element.
Protective seam is peeled, this photosensitive element of heat lamination on whole copper clad laminate from photosensitive element obtained above.Then, make to have the pore size shown in Fig. 2 be 100 μm and between hole separate spacing be the pattern of 100 μm or pore size be 80 μm and between hole separate negative mask that spacing is the pattern of 80 μm and film closely sealed, use ultraviolet exposure apparatus according ((strain) HITECH system, trade name: HTE-5102S) to expose with the predetermined degree of exposure shown in table 6.Then, use the aqueous sodium carbonate of 1 quality % with 0.18MPa (1.8kgf/cm 2) press atomization develop 60 seconds, development is dissolved in unexposed portion.Then, use ultraviolet exposure apparatus according ((strain) GSYUASALighting system, trade name: conveyor-type UV irradiation unit) with 1000mJ/cm 2exposure expose after, with 150 DEG C heating 1 hour, make test film.Use the test film of gained, carry out the evaluation same with embodiment 31.Evaluation result is shown in table 6.
[table 1]
Table 1
* 1: refer to the solution (solid component concentration: 60 quality %) containing epoxy resin (I).
* 2: refer to the solution (solid component concentration: 60 quality %) containing epoxy resin (II)-a.
* 3: exposure 600mJ/cm during development 2time evaluation.
Note) detailed content of each material is as described below in table 1.
IRGACURE819: two (2,4,6 ?trimethylbenzoyl) phenylphosphine oxide (BASF Japan (strain) system, trade name)
DAROCURTPO:2,4,6-trimethylbenzoyldiphenyl oxide (BASF Japan (strain) system, trade name)
IRGACURE907:2-methyl-[4-(methyl mercapto) phenyl] morpholino-1-acetone (BASF Japan (strain) system, trade name)
IRGACUREOXE01:(1,2-acetyl caproyl, and 1-[4-(thiophenyl)-, 2-(o-benzoyl oximes)] (BASF Japan (strain), trade name)
KAYARADDPHA: Dipentaerythritol Pentaacrylate (Japanese chemical drug (strain) system, trade name)
BaSO 4: Sakai chemical industry (strain) is made
SiO 2: (strain) imperial gloomy system
EPIKOTE828: bisphenol A type epoxy resin (Mitsubishi Chemical's (strain) system, trade name)
Results verification as shown in Table 1, the photosensitive polymer combination of the present invention of embodiment 1 ~ 6, even if the pattern of permanent mask resist (solder resist) is pore size 100 μm and the pattern separating spacing 100 μm between hole or pore size 80 μm and separate the such fine pattern of spacing 80 μm between hole, also excellent surface cure and bottom curability can be maintained, the hole shape of resist shape excellence can be obtained, that can also reduce around pattern is thicker, and aperture precision is excellent.Also confirm in addition, not only have excellent resist shape, other proterties such as solder heat resistance are also excellent.This effect can thought to use photosensitive polymer combination of the present invention, especially (B) acylphosphine oxide system Photoepolymerizationinitiater initiater and the combination as (C1) alkyl amino benzene derivative of hydrogen donor and obtain.
And in comparative example 1 ~ 4, eliminate bottom curability and the problem of resist shape, in addition, thicker around the pattern that also there occurs permanent mask resist (solder resist) is insufficient result.
[table 2]
Table 2
* 1: refer to the solution (solid component concentration: 60 quality %) containing epoxy resin (I).
* 2: refer to the solution (solid component concentration: 60 quality %) containing epoxy resin (II)-a.
* 3: exposure 600mJ/cm during development 2time evaluation.
Note) detailed content of each material is as described below in table 2.
IRGACURE819: two (2,4,6 ?trimethylbenzoyl) phenylphosphine oxide (BASF Japan (strain) system, trade name)
DAROCURTPO:2,4,6-trimethylbenzoyldiphenyl oxide (BASF Japan (strain) system, trade name)
IRGACURE907:2-methyl-[4-(methyl mercapto) phenyl] morpholino-1-acetone (BASF Japan (strain) system, trade name)
IRGACURE369:2-benzoyl-2-dimethylamino-1-(4-morpholino-phenyl) butanone-1 (BASF Japan (strain) system, trade name)
Pyrazoline system sensitizer: 1-phenyl-3-(4-tert-butyl-styrene base)-5-(4-tbutyl-phenyl)-pyrazoline
EAB:4,4 '-diethylamino benzophenone (hodogaya chemical (strain) system)
DETX-S:2,4-diethyl thioxanthone (Japanese chemical drug (strain) system)
KAYARADDPHA: Dipentaerythritol Pentaacrylate (Japanese chemical drug (strain) system, trade name)
BaSO 4: Sakai chemical industry (strain) is made
SiO 2: (strain) imperial gloomy system
EPIKOTE828: bisphenol A type epoxy resin (Mitsubishi Chemical's (strain) system, trade name)
Result is as shown in Table 2 known, the photosensitive polymer combination of the present invention of embodiment 7 ~ 12, even if be digit explosure, luminous sensitivity is also excellent, maintains bottom curability, obtains the hole shape of resist shape excellence.Confirm in addition, even if the pattern of permanent mask resist (solder resist film) is pore size 100 μm and the pattern separating spacing 100 μm between hole or pore size 80 μm and separate the such fine pattern of spacing 80 μm between hole, also can reduce the thicker of surrounding, aperture precision is excellent.Also confirm in addition, not only have excellent resist shape, other proterties such as solder heat resistance are also excellent.This effect can thought to use the combination of photosensitive polymer combination of the present invention, especially (B) acylphosphine oxide system Photoepolymerizationinitiater initiater and (C2) pyrazoline system sensitizer and obtain.
And in comparative example 5 ~ 12, do not eliminate the problem of bottom curability and resist shape, in addition, the pattern (pore size 100 μm and the pattern separating spacing 100 μm between hole or pore size 80 μm and the pattern at 80 μm, interval between hole) that also there occurs permanent mask resist (solder resist) around thicker is insufficient result.
[table 3]
Table 3
* 1: refer to the solution (solid component concentration: 60 quality %) containing epoxy resin (I).
* 2: refer to the solution (solid component concentration: 60 quality %) containing epoxy resin (II)-a.
* 3: refer to the solution (solid component concentration: 60 quality %) containing epoxy resin (IV)-a.
* 4: exposure 600mJ/cm during development 2time evaluation.
Note) detailed content of each material is as described below in table 3.
IRGACURE819: two (2,4,6 ?trimethylbenzoyl) phenylphosphine oxide (BASF Japan (strain) system, trade name)
DAROCURTPO:2,4,6-trimethylbenzoyldiphenyl oxide (BASF Japan (strain) system, trade name)
IRGACURE907:2-methyl-[4-(methyl mercapto) phenyl] morpholino-1-acetone (BASF Japan (strain) system, trade name)
Anthracene system sensitizer 1:9,10-dibutoxy anthracene
Anthracene system sensitizer 2:9,10-diethoxy anthracene
Anthracene system sensitizer 3:9,10-dipropoxy anthracene
EAB:4,4 '-diethylamino benzophenone (hodogaya chemical (strain) system)
DETX-S:2,4-diethyl thioxanthone (Japanese chemical drug (strain) system)
KAYARADDPHA: Dipentaerythritol Pentaacrylate (Japanese chemical drug (strain) system, trade name)
BaSO 4: Sakai chemical industry (strain) is made
SiO 2: (strain) imperial gloomy system
EPIKOTE828: bisphenol A type epoxy resin (Mitsubishi Chemical's (strain) system, trade name)
Results verification as shown in Table 3 arrives, the photosensitive polymer combination of the present invention of embodiment 13 ~ 18 has excellent photo-curable, even if the pattern of permanent mask resist (solder resist) is pore size 100 μm and the pattern separating spacing 100 μm between hole or pore size 80 μm and separate the such fine pattern of spacing 80 μm between hole, also there is excellent bottom curability, unconfirmed to undercutting, hangover or thicker, or the rectilinearity of pattern contour is not poor, can obtain excellent resist shape, aperture precision is excellent.Also confirm in addition, not only have excellent solder heat resistance and resistance to solder flux corrosivity, the various performances such as adaptation, solvent resistance, chemical reagent resistance (acid resistance, alkali resistance) are also excellent.
And in comparative example 13 ~ 20, photo-curable and bottom curability low, resist shape presents undercutting, resist shape difference.
[table 4]
Table 4
* 1: refer to the solution (solid component concentration: 60 quality %) containing epoxy resin (I).
* 2: refer to the solution (solid component concentration: 60 quality %) containing epoxy resin (II)-a.
* 3: exposure 600mJ/cm during development 2time evaluation.
Note) detailed content of each material is as described below in table 4.
IRGACURE819: two (2,4,6 ?trimethylbenzoyl) phenylphosphine oxide (BASF Japan (strain) system, trade name)
DAROCURTPO:2,4,6-trimethylbenzoyldiphenyl oxide (BASF Japan (strain) system, trade name)
IRGACURE907:2-methyl-[4-(methyl mercapto) phenyl] morpholino-1-acetone (BASF Japan (strain) system, trade name)
Imidazoles: 2-(Chloro-O-Phenyl)-4,5-diphenyl-imidazole dimer
Two (9, the 9 '-acridinyl) heptane of acridine: 1,7-
Two luxuriant titaniums: two (η 5-cyclopentadienyl group)-bis-(the fluoro-3-of 2,6-bis-(1H-pyrroles-1-base) phenyl) titanium
IRGACUREOXE01:(1,2-acetyl caproyl, and 1-[4-(thiophenyl)-, 2-(o-benzoyl oximes)] (BASF Japan (strain) system, trade name)
KAYARADDPHA: Dipentaerythritol Pentaacrylate (Japanese chemical drug (strain) system, trade name)
BaSO 4: Sakai chemical industry (strain) is made
SiO 2: (strain) imperial gloomy system
EPIKOTE828: bisphenol A type epoxy resin (Mitsubishi Chemical's (strain) system, trade name)
Results verification as shown in Table 4 arrives, the photosensitive polymer combination of the present invention of embodiment 19 ~ 24, bottom curability can be maintained, the hole shape obtaining resist shape excellence can be stablized, even if the pattern of permanent mask resist (solder resist) is pore size 100 μm and the pattern separating spacing 100 μm between hole or pore size 80 μm and separate the such fine pattern of spacing 80 μm between hole, also can reduce the thicker of surrounding, aperture precision is excellent.Also confirm in addition, not only have excellent resist shape, other proterties such as solder heat resistance are also excellent.This effect can thought to use the combination of photosensitive polymer combination of the present invention, especially (B) acylphosphine oxide system Photoepolymerizationinitiater initiater and (C3) Photoepolymerizationinitiater initiater and obtain.
And in comparative example 21 ~ 24, eliminate bottom curability and the problem of resist shape, in addition, thicker around the pattern that also there occurs permanent mask resist is insufficient result.
[table 5]
Table 5
* 1: refer to the solution (solid component concentration: 60 quality %) containing epoxy resin (I).
* 2: refer to the solution (the solid constituent degree of depth: 60 quality %) containing epoxy resin (II)-a.
* 3: refer to the solution (solid component concentration: 60 quality %) containing epoxy resin (IV)-a.
* 4: refer to the solution (the solid constituent degree of depth: 60 quality %) containing epoxy resin (IV)-b.
Note) detailed content of each material is as described below in table 5.
IRGACURE819: two (2,4,6 ?trimethylbenzoyl) phenylphosphine oxide (BASF Japan (strain) system, trade name)
DAROCURTPO:2,4,6-trimethylbenzoyldiphenyl oxide (BASF Japan (strain) system, trade name)
IRGACURE907:2-methyl-[4-(methyl mercapto) phenyl] morpholino-1-acetone (BASF Japan (strain) system, trade name)
IRGANOX1010: pentaerythrite four [3-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester] (BASF Japan (strain) system, trade name)
IRGANOX1035: thiodiethylene two [3-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester] (BASF Japan (strain) system, trade name)
IRGANOX1076: octadecyl [3-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester] (BASF Japan (strain) system, trade name)
KAYARADDPHA: Dipentaerythritol Pentaacrylate (Japanese chemical drug (strain) system, trade name)
BaSO 4: Sakai chemical industry (strain) is made
SiO 2: (strain) imperial gloomy system
EPIKOTE828: bisphenol A type epoxy resin (Mitsubishi Chemical's (strain) system, trade name)
Results verification as shown in Table 5 arrives, the photosensitive polymer combination of the present invention of embodiment 25 ~ 30, even if the pattern of permanent mask resist (solder resist) is pore size 100 μm and the pattern separating spacing 100 μm between hole or pore size 80 μm and separate the such fine pattern of spacing 80 μm between hole, also excellent surface cure and bottom curability can be maintained, unconfirmed to undercutting, hangover or thicker, or the rectilinearity of pattern contour is not poor, can obtain excellent resist shape, aperture precision is excellent.In addition, not only have excellent solder heat resistance and resistance to solder flux corrosivity, the various performances such as adaptation, solvent resistance, chemical reagent resistance (acid resistance, alkali resistance) are also excellent.
And in comparative example 25 ~ 30, surface cure and bottom curability low, resist shape presents undercutting, in comparative example 29 and 30, by increasing illuminated line amount during development, although surface cure and bottom curability are well, halation becomes large, the live width in the pars intermedia (central part) of patterned section and most deep (bottom) is greater than the live width on surface element (top), and resist shape worsens.
[table 6]
Table 6
* 1: refer to the solution (solid component concentration: 73 quality %) containing epoxy resin (IV)-c.
* 2: refer to the solution (solid component concentration: 62 quality %) containing epoxy resin (II)-b.
* 3: exposure 600mJ/cm during development 2time evaluation.
Note) detailed content of each material is as described below in table 6.
IRGACURE819: two (2,4,6-trimethylbenzoyl) phenylphosphine oxide (BASF Japan (strain) system, trade name)
IRGACURE907:2-methyl-[4-(methyl mercapto) phenyl] morpholino-1-acetone (BASF Japan (strain) system, trade name)
DETX-S:2,4-diethyl thioxanthone (Japanese chemical drug (strain) system, trade name)
MBI: mercaptobenzimidazole
Phthualocyanine pigment: adret pigment (strain) is made
ARONIXM402: dipentaerythritol acrylate (East Asia synthesis (strain) system, trade name)
BaSO 4: Sakai chemical industry (strain) is made
SiO 2: (strain) imperial gloomy system
YSLV-80XY: tetramethyl bisphenol f type epoxy resin (Nippon Steel's chemistry (strain) system, trade name)
RE-306: phenolic varnish type polyfunctional epoxy resin (Japanese chemical drug (strain) system, trade name)
PB-3600: epoxidized polybutadiene (Daicel chemistry (strain) system, trade name)
SP1108: vibrin (Hitachi changes into (strain) system, trade name)
DICY7: dicyandiamide
Results verification as shown in Table 6 arrives, the photosensitive polymer combination of the present invention of embodiment 31 ~ 34, even if the pattern of photosensitive element and permanent mask resist (solder resist) is pore size 100 μm and the pattern separating spacing 100 μm between hole or pore size 80 μm and separate the such fine pattern of spacing 80 μm between hole, also unconfirmed to undercutting, hangover or thicker, or the rectilinearity of pattern contour is not poor, excellent resist shape can be obtained.
In addition, chemically-resistant plating, solder heat resistance, resistance to anti-thread breakage, the various performance such as adaptation, solvent resistance, chemical reagent resistance (acid resistance, alkali resistance) is also excellent.
And the photosensitive polymer combination of comparative example 31 ~ 34, resist shape worsens, and solder heat resistance and resistance to anti-thread breakage also poor.
Industrial applicibility
According to the present invention, the disappearance that do not produce the undercutting that is cut off of bottom and resist top can be obtained and can form that the rectilinearity of pattern contour is good and resist shape is excellent, the photosensitive polymer combination of the pattern of excellent in resolution, can be formed through the permanent mask resist separating the pattern of the formation excellent in stability of spacing between the pore size and hole of miniaturization.Permanent mask resist is suitably used for printing distributing board.

Claims (15)

1. a photosensitive polymer combination, sour modification that it comprises (A) is containing vinyl epoxy resin, (B) acylphosphine oxide system Photoepolymerizationinitiater initiater, (C) adjuvant and (D) photopolymerizable compound, and described (C) adjuvant is be selected from least one in following material: (C1) alkyl amino benzene derivative; (C2) pyrazoline system sensitizer or anthracene system sensitizer; (C3) at least one Photoepolymerizationinitiater initiater in imidazoles system Photoepolymerizationinitiater initiater, acridine system Photoepolymerizationinitiater initiater and two luxuriant titanium system Photoepolymerizationinitiater initiaters is selected from; (C4) at least one antioxidant in hindered phenol system antioxidant, quinone system antioxidant, amine system antioxidant, sulphur system antioxidant and phosphorous antioxidant is selected from; And (C5) sulfur-bearing alcohol-based compounds.
2. photosensitive polymer combination according to claim 1, (A) sour modification is resin resin (a ') being reacted with the multi-anhydride (c) containing saturated base or unsaturated group and obtains containing vinyl epoxy resin, wherein resin (a ') is by making epoxy resin (a) and obtaining containing vinyl monocarboxylic acid (b) reaction
Described epoxy resin (a) being selected from has the epoxy resin of the structural unit represented by general formula (I), the epoxy resin with the structural unit represented by general formula (II), the epoxy resin with the structural unit represented by general formula (III), the bis-phenol phenolic resin varnish type epoxy resin with the structural unit represented by general formula (IV) and at least one had in the bis-phenol phenolic resin varnish type epoxy resin of the structural unit represented by general formula (V)
[changing 1]
In formula (I), R 11represent hydrogen atom or methyl, Y 1represent glycidyl,
[changing 2]
In formula (II), R 12represent hydrogen atom or methyl, Y 2represent glycidyl, multiple R 12can be the same or different,
[changing 3]
In formula (III), Y 3represent hydrogen atom or glycidyl, at least one Y 3represent glycidyl, multiple Y 3can be the same or different,
[changing 4]
In formula (IV), R 13represent hydrogen atom, alkyl, aryl, aralkyl, sulfonic group or trihalomethyl, Y 4represent hydrogen atom or glycidyl, at least one Y 4represent glycidyl, multiple R 13can be the same or different,
[changing 5]
In formula (V), R 14represent hydrogen atom, alkyl, aryl, aralkyl, sulfonic group or trihalomethyl, Y 5represent hydrogen atom or glycidyl, at least one Y 5represent glycidyl, multiple R 14can be the same or different.
3. photosensitive polymer combination according to claim 1 and 2, (B) acylphosphine oxide system Photoepolymerizationinitiater initiater is for being selected from (2, 6-Dimethoxybenzoyl)-2, 4, 6-trimethylbenzoyl-amyl group phosphine oxide, two (2, 4, 6-trimethylbenzoyl)-phenylphosphine oxide, 2, 4, 6-trimethylbenzoyldiphenyl oxide, ethyl-2, 4, 6-trimethylbenzoyl phenyl phosphinate, two (2, 4, 6-trimethylbenzoyl)-phenylphosphine oxide, (2, 5-dihydroxy phenyl) diphenyl phosphine oxide, (p-hydroxybenzene) diphenyl phosphine oxide, at least one in two (p-hydroxybenzene) phenylphosphine oxide and three (p-hydroxybenzene) phosphine oxide.
4., according to the photosensitive polymer combination in claims 1 to 3 described in wantonly 1, (C) adjuvant is at least one (C1) the alkyl amino benzene derivative be selected from phenylglycine derivatives, aminobenzoic acid derivative and aminobenzoic acid ester derivant.
5. according to the photosensitive polymer combination in claims 1 to 3 described in wantonly 1, (C2) pyrazoline system sensitizer of (C) adjuvant represented by following general formula (VI),
[changing 6]
In formula (VI), R represents the alkyl of carbon number 4 ~ 12, and a, b and c represent the integer of 0 ~ 2 respectively, when the summation of a, b and c is 1 ~ 6, a, the summation of b and c is 2 ~ 6, can be the same or different respectively with the multiple R in a part.
6., according to the photosensitive polymer combination in claims 1 to 3 described in wantonly 1, (C) adjuvant is at least one (C2) the anthracene system sensitizer be selected from dialkyl group anthracene, diphenylanthrancene and dialkoxy anthracene.
7., according to the photosensitive polymer combination in claims 1 to 3 described in wantonly 1, (C) adjuvant is for being selected from 2,4,5-triarylimidazoles dimer, 1,7-two (9,9 '-acridinyl) heptane, two (η 5-cyclopentadienyl group)-bis-(2, the fluoro-3-of 6-bis-(1H-pyrroles-1-base) phenyl) titanium and two (2,4-cyclopentadienyl group) at least one (C3) Photoepolymerizationinitiater initiater in-bis-(the fluoro-3-of 2,6-bis-(1-pyrrole radicals) phenyl) titanium.
8., according to the photosensitive polymer combination in claims 1 to 3 described in wantonly 1, (C) adjuvant is at least one (C4) antioxidant be selected from hindered phenol system antioxidant, sulphur system antioxidant and phosphorous antioxidant.
9., according to the photosensitive polymer combination in claims 1 to 3 described in wantonly 1, (C) adjuvant is at least one (C5) the sulfur-bearing alcohol-based compounds in selected from mercapto benzoxazole, mercaptobenzothiazoler and mercaptobenzimidazole.
10., according to the photosensitive polymer combination in claim 1 ~ 9 described in wantonly 1, described (D) photopolymerizable compound is the compound containing (methyl) acryloyl group.
11. according to the photosensitive polymer combination in claim 1 ~ 10 described in wantonly 1, further containing (E) inorganic filler.
12. according to the photosensitive polymer combination in claim 1 ~ 11 described in wantonly 1, and it is for the formation of permanent mask resist.
13. 1 kinds of photosensitive elements, its photographic layer that there is supporter and use the photosensitive polymer combination in claim 1 ~ 12 described in wantonly 1 to be formed on this supporter.
14. 1 kinds of permanent mask resists, it is formed by the photosensitive polymer combination in claim 1 ~ 12 described in wantonly 1.
15. 1 kinds of printing distributing boards, it has permanent mask resist according to claim 14.
CN201480042096.6A 2013-08-02 2014-08-01 Photosensitive-resin composition Pending CN105431778A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1945429A (en) * 2005-10-05 2007-04-11 旭化成电子材料元件株式会社 Photosensitive resin composition and photosensitive resin laminate using the same
CN101681107A (en) * 2007-05-11 2010-03-24 日立化成工业株式会社 Photosensitive resin composition, photosensitive element, method of forming resist pattern, and process for producing printed wiring board
CN102138104A (en) * 2008-09-04 2011-07-27 日立化成工业株式会社 Photosensitive resin composition for protective film of printed wiring board for semiconductor package
CN102385247A (en) * 2010-09-01 2012-03-21 住友化学株式会社 Photosensitive resin composition

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3247091B2 (en) 1997-11-28 2002-01-15 日立化成工業株式会社 Photocurable resin composition and photosensitive element using the same
JP4240885B2 (en) 2001-12-28 2009-03-18 日立化成工業株式会社 Method for forming protective film of flexible wiring board
JP4651524B2 (en) * 2005-07-22 2011-03-16 富士フイルム株式会社 Pattern forming material, pattern forming apparatus and pattern forming method
JP2007078890A (en) * 2005-09-12 2007-03-29 Fujifilm Corp Photosensitive composition, pattern forming material, photosensitive laminate, pattern forming apparatus and pattern forming method
JP4708238B2 (en) * 2006-03-24 2011-06-22 富士フイルム株式会社 Photosensitive film, permanent pattern forming method, and printed circuit board
JP5031578B2 (en) * 2006-03-29 2012-09-19 太陽ホールディングス株式会社 Photocurable / thermosetting resin composition, cured product thereof, and printed wiring board obtained using the same
JP2010235739A (en) 2009-03-31 2010-10-21 Toyo Ink Mfg Co Ltd Photosensitive black composition
JP5325805B2 (en) * 2010-01-29 2013-10-23 株式会社タムラ製作所 Photosensitive resin composition and printed wiring board using cured film thereof
KR101151244B1 (en) 2010-06-07 2012-06-14 고려대학교 산학협력단 Apparatus and method for monitoring of airgap eccentricity of induction motors, and a medum having computer readable program for executing the method

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1945429A (en) * 2005-10-05 2007-04-11 旭化成电子材料元件株式会社 Photosensitive resin composition and photosensitive resin laminate using the same
CN101681107A (en) * 2007-05-11 2010-03-24 日立化成工业株式会社 Photosensitive resin composition, photosensitive element, method of forming resist pattern, and process for producing printed wiring board
CN102138104A (en) * 2008-09-04 2011-07-27 日立化成工业株式会社 Photosensitive resin composition for protective film of printed wiring board for semiconductor package
CN102385247A (en) * 2010-09-01 2012-03-21 住友化学株式会社 Photosensitive resin composition

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111406233A (en) * 2017-12-06 2020-07-10 日本化药株式会社 Photosensitive resin composition, dry film resist, and cured product of resin composition and dry film resist
CN111406233B (en) * 2017-12-06 2023-12-26 日本化药株式会社 Photosensitive resin composition, dry film resist and cured product thereof
WO2019173966A1 (en) * 2018-03-13 2019-09-19 Hitachi Chemical Company, Ltd. Photosensitizer, photosensitive resin composition, photosensitive element, and method of producing wiring board
WO2019173967A1 (en) * 2018-03-13 2019-09-19 Hitachi Chemical Company, Ltd. Photosensitizer, photosensitive resin composition, photosensitive element, and method of producing wiring board
CN108957954A (en) * 2018-08-03 2018-12-07 广东泰亚达光电有限公司 A kind of new pattern laser directly retouches imaging dry film and preparation method thereof
CN111624852A (en) * 2019-02-28 2020-09-04 东京应化工业株式会社 Photosensitive resin composition and method for etching glass substrate

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