CN107652383A - Photosensitive polymer combination, photosensitive element, the manufacture method of the forming method of resist pattern and printed circuit board (PCB) - Google Patents

Photosensitive polymer combination, photosensitive element, the manufacture method of the forming method of resist pattern and printed circuit board (PCB) Download PDF

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Publication number
CN107652383A
CN107652383A CN201710953268.0A CN201710953268A CN107652383A CN 107652383 A CN107652383 A CN 107652383A CN 201710953268 A CN201710953268 A CN 201710953268A CN 107652383 A CN107652383 A CN 107652383A
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Prior art keywords
polymer combination
photosensitive polymer
photosensitive
methyl
resist pattern
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Inventor
宫坂昌宏
锻治诚
村上泰治
印杰
姜学松
李宝
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Shanghai Jiaotong University
Showa Denko Materials Co ltd
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Shanghai Jiaotong University
Hitachi Chemical Co Ltd
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Priority claimed from JP2011283988A external-priority patent/JP5799799B2/en
Application filed by Shanghai Jiaotong University, Hitachi Chemical Co Ltd filed Critical Shanghai Jiaotong University
Publication of CN107652383A publication Critical patent/CN107652383A/en
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    • 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
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • 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
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • 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
    • C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
    • C08F257/02—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00 on to polymers of styrene or alkyl-substituted styrenes
    • 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
    • G03F7/0035—Multiple processes, e.g. applying a further resist layer on an already in a previously step, processed pattern or textured surface

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Architecture (AREA)
  • Structural Engineering (AREA)
  • Materials For Photolithography (AREA)

Abstract

The present invention relates to the manufacture method of a kind of photosensitive polymer combination, photosensitive element, the forming method of resist pattern and printed circuit board (PCB), the photosensitive polymer combination contains (A) binder polymer, (B) photopolymerizable compound and (C) Photoepolymerizationinitiater initiater, wherein, (C) Photoepolymerizationinitiater initiater includes the compound represented by following formula (1).In formula, R1And R2The group shown in following formula (1a) or (1b) is represented independently of one another, and R represents the alkyl or phenyl of carbon number 1~20 independently of one another, and multiple R can be with identical also different.

Description

Photosensitive polymer combination, photosensitive element, the forming method and print of resist pattern The manufacture method of printed circuit board
The present invention be Application No. 2012104018414, the applying date be on October 19th, 2012, entitled " photosensitive The patent application of property resin combination, photosensitive element, the manufacture method of the forming method of resist pattern and printed circuit board (PCB) " Divisional application.
Invention field
The present invention relates to photosensitive polymer combination and the formation side of its photosensitive element, resist pattern is used The manufacture method of method and printed circuit board (PCB).
Background technology
In the manufacturing field of printed circuit board (PCB), as the anticorrosive additive material used in etching or plating, widely use photosensitive Property resin combination.Photosensitive polymer combination is used as photosensitive element (layered product), the photosensitive element (stacking mostly Body) possess support membrane and the layer (hereinafter referred to as " photoresist formed using photosensitive polymer combination on the support membrane Composition layer ").
Printed circuit board (PCB) is for example operated and manufactured as described below.First, it is laminated (lamination) on circuit formation substrate The photosensitive polymer combination layer (lamination process) of photosensitive element.Then, support membrane is peeled off after removing, to photoresist The established part of composition layer irradiates active ray and exposure portion is solidified (exposure process).Thereafter, remove from substrate and do not expose Light portion (development), so as to form the resist pattern formed by the solidfied material of photosensitive polymer combination (development work on substrate Sequence).Implement etching process or plating for the resist pattern that is obtained and form after circuit that (circuit forms work on substrate Sequence), finally peel off and remove resist and manufacture printed circuit board (PCB) (stripping process).
As the method for exposure, used always in the past using mercury vapor lamp as light source by photomask the side that is exposed Method, but begin to use referred to as DLP (optical digital computing, Digital Light Processing) or LDI (laser straights in recent years Be connected into picture, Laser Direct Imaging), the numerical data of pattern is depicted in direct exposure resin composition layer Directly describe exposure method.This directly describe exposure method because aligned in position ratio of precision is more good by the exposure method of photomask and The pattern of fine can be obtained, therefore is especially directed in the making of high-density packages substrate.
However, various characteristics are required in photosensitive polymer combination.For example, in exposure process, in order to improve Production efficiency is, it is necessary to shorten the time for exposure.However, in above-mentioned direct description exposure method, except light source uses the monochromes such as laser Outside light, also while being scanned one side irradiation light to substrate, therefore it there are and the conventional exposure side by photomask Method is compared to the tendency for needing more time for exposure.Therefore, improve production efficiency to shorten the time for exposure, it is necessary to it is conventional Compared to the sensitivity for improving photosensitive polymer combination.
For these requirements, various photosensitive polymer combinations were have studied in the past.For example, Japanese Unexamined Patent Publication 2007-279381 Number publication, No. 07/004619 pamphlet of International Publication No., No. 10/126006 pamphlet of International Publication No., International Publication No. 09/ Disclosed in No. 147031 pamphlets, Japanese Unexamined Patent Application Publication 2010-526846 publications and Japanese Unexamined Patent Application Publication 2010-527338 publications The photosensitive polymer combination of sensitivity etc. is improved by using specific Photoepolymerizationinitiater initiater or sensitizing coloring matter.
The content of the invention
Along with the densification of printed circuit board (PCB) in recent years, the sense for resolution (resolution) and excellent adhesion The requirement of photosensitive resin composition is being increased.Particularly, in the making of package substrate, it is desirable to L/S (line widths/interval can be formed Width) it is 10/10 (unit：μm) left and right resist pattern photosensitive polymer combination.
But conventional photosensitive element is reaching high sensitivity while is forming resolution and excellent adhesion There is room for improvement in terms of resist pattern.
The present invention in view of above-mentioned problem of the prior art and carry out, there is provided sensitivity, resolution and excellent adhesion Photosensitive polymer combination and its photosensitive element, the forming method of resist pattern and printed circuit board (PCB) are used Manufacture method.
The present invention provides a kind of photosensitive polymer combination, and it contains (A) binder polymer, (B) optical polymerism chemical combination Thing and (C) Photoepolymerizationinitiater initiater, wherein, (C) Photoepolymerizationinitiater initiater includes the compound shown in following formula (1).
In formula (1), R1And R2The group shown in following formula (1a) or (1b) is represented independently of one another.
In formula (1a) and (1b), R represents the alkyl or phenyl of carbon number 1~20 independently of one another, and multiple R can With it is identical also can be different.
By above-mentioned formula (1) represent compound not only for 350~365nm of wavelength light, and for wavelength 390~ 410nm light also has bigger absorption, therefore the photosensitive polymer combination of the present invention is for 350~410nm's of wavelength Light can obtain good sensitivity.In addition, by comprising the compound represented by above-mentioned formula (1), can not only make the sense of the present invention Sensitivity, resolution and the excellent adhesion of photosensitive resin composition, and peel property, plating formative and plating can be made Cover contaminative raising.
In addition, in the photosensitive polymer combination of the present invention, the maximum absorption wavelength of the compound represented by above-mentioned formula (1) Preferably 350~410nm.Good sensitivity, while wavelength 500nm can be obtained accordingly, for 350~410nm of wavelength light Absorption at long wavelength side above tails off, and the stability under gold-tinted becomes good.
In addition, in the photosensitive polymer combination of the present invention, preferably above-mentioned (A) binder polymer contains (methyl) propylene Acid and styrene or styrene derivative are as copolymer composition.Thus, the alkali-developable of photosensitive polymer combination, resolution And adaptation further improves.
In addition, the present invention provides a kind of photosensitive element, it possess support membrane and formed on the support membrane by above-mentioned The photosensitive polymer combination layer that photosensitive polymer combination is formed.By using such photosensitive element, so as to efficient Ground forms sensitivity, resolution, adaptation, peel property, plating formative and all good resist pattern of plating contaminative.
In addition, the present invention provides a kind of forming method of resist pattern, it includes following process：Stacking is by upper on substrate State the lamination process of the photosensitive polymer combination layer of photosensitive polymer combination formation, the rule to photosensitive polymer combination layer Determine the exposure process of partial illumination active ray and from substrate remove photosensitive polymer combination layer above-mentioned established part with Outer part is so as to the developing procedure of the resist pattern that formation is formed by the solidfied material of photosensitive polymer combination on substrate.Root According to the above method, sensitivity, resolution, adaptation, peel property, plating formative and plating contaminative can be efficiently formed All good resist pattern.
In addition, the present invention provides a kind of manufacture method of printed circuit board (PCB), its include to by the above method and formed with The substrate of resist pattern is etched or the process of plating.According to the manufacture method, high-density packages substrate can be efficiently manufactured The printed circuit board (PCB) of such wiring with densification.
According to the present invention, it is possible to provide sensitivity, resolution and excellent adhesion photosensitive polymer combination and make With the manufacture method of its photosensitive element, the forming method of resist pattern and printed circuit board (PCB).
Brief description of the drawings
Fig. 1 is the pattern sectional view for an embodiment for representing photosensitive element, and Fig. 2 is the production for representing present embodiment Thing (C-1)1The figure of H-NMR spectrum.
Symbol description
1 photosensitive element, 2 support membranes, 3 photosensitive polymer combination layers, 4 diaphragms.
Embodiment
Hereinafter, the preferred forms for implementing the present invention are described in detail.But the present invention is not only restricted to following Embodiment.It is explained, in this manual, (methyl) acrylic acid refers to acrylic or methacrylic acid, (methyl) third Olefin(e) acid ester refers to acrylate or methacrylate, and (methyl) acryloyl group refers to acryloyl group or methylacryloyl.Separately Outside, (poly-) ethylene oxide chain refers to oxyethylene group or polyethylene oxide chain, (poly-) propylene oxide chain refer to oxypropylene group or PPOX chain.Further " EO modifications " refers to the compound with (poly-) ethylene oxide chain, and " PO modifications " refers to have The compound of (poly-) propylene oxide chain, " EOPO modifications " refer to have (poly-) ethylene oxide chain and (poly-) propylene oxide chain this Both compounds.
(photosensitive polymer combination)
The photosensitive polymer combination of present embodiment contain (A) binder polymer, (B) photopolymerizable compound and (C) Photoepolymerizationinitiater initiater, (C) Photoepolymerizationinitiater initiater include the compound represented by above-mentioned formula (1).
First, to being illustrated as the binder polymer of (A) composition.As (A) binder polymer, such as can arrange Enumerate acrylic resin, phenylethylene resin series, epoxy system resin, acid amides system resin, amide epoxy system resin, alkyd system resin And phenolic aldehyde system resin.From the viewpoint of alkali-developable, preferred acrylic resin.They may be used alone or in combination use Two or more.
(A) binder polymer for example can be by making polymerizable monomer carry out radical polymerization to manufacture.As above-mentioned poly- Conjunction property monomer, such as styrene, vinyltoluene, α-methylstyrene, p-methylstyrene, p -ethyl-styrene can be included Etc. polymerizable styrene derivative, (methyl) acrylic acid, α-bromine (methyl) acrylic acid, α-chlorine (methyl) acrylic acid, β-furans Base (methyl) acrylic acid, β-styryl (methyl) acrylic acid, (methyl) alkyl acrylate, (methyl) acrylate base Ester, (methyl) benzyl acrylate, (methyl) acrylic acid furfuryl group ester, (methyl) acrylic acid tetrahydro furfuryl ester, (methyl) acrylic acid two Methylamino ethyl ester, (methyl) acrylic acid diethylamino ethyl ester, (methyl) glycidyl acrylate, 2,2,2- trifluoroethyls (methyl) acrylic monomers such as (methyl) acrylate, 2,2,3,3- tetra- fluoropropyl (methyl) acrylate, vinyl-positive fourth The alkyl ether of the vinyl alcohols such as base ether, maleic acid, maleic anhydride, monomethyl maleate, ethyl maleate, maleic acid list isopropyl The maleic acid such as ester system monomer, acrylamide, acrylonitrile, fumaric acid, cinnamic acid, alpha-cyano cinnamic acid, itaconic acid, crotonic acid and Propiolic acid.They may be used alone or in combination two or more to use.
As above-mentioned (methyl) alkyl acrylate, such as (methyl) methyl acrylate, (methyl) acrylic acid can be included Ethyl ester, (methyl) n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) acrylic acid uncle Butyl ester, (methyl) amyl acrylate, (methyl) Hexyl 2-propenoate, (methyl) heptylacrylate, (methyl) 2-ethyl hexyl acrylate, (first Base) 2-ethylhexyl acrylate and their constitutional isomer.They, which may be used alone or in combination, uses two or more.
(A) binder polymer preferably comprises carboxyl from the viewpoint of alkali-developable, such as can be by making with carboxyl Polymerizable monomer and other polymerizable monomers carry out radical polymerization to manufacture.As the above-mentioned polymerism list with carboxyl Body, preferably (methyl) acrylic acid.
(A) binder polymer preferably comprises styrene or styrene derivative is made from the viewpoint of adaptation raising For copolymer composition.In the case of containing above-mentioned styrene or styrene derivative as copolymer composition, improved well from balance From the viewpoint of adaptation and peel property, its content preferably comprises 5~70 relative to the nonvolatile component entirety of (A) composition Quality %, more preferably comprising 10~65 mass %, more preferably comprising 15~60 mass %.From the viewpoint of excellent adhesion Preferably more than 5 mass %, more preferably more than 10 mass %, more preferably more than 15 mass %.It is excellent from peel property From the viewpoint of be preferably below 70 mass %, more preferably below 65 mass %, more preferably below 60 mass %.
In addition, (A) binder polymer preferably comprises (methyl) benzyl acrylate as copolymer composition.Contain (methyl) third In the case that olefin(e) acid benzyl ester is as copolymer composition, from the viewpoint of balance improves resolution and peel property well, its Content is all relative to the nonvolatile component of (A) composition, preferably comprises 5~70 mass %, more preferably comprising 10~65 mass %, More preferably include 15~60 mass %.From resolution it is excellent from the viewpoint of be preferably more than 5 mass %, more preferably 10 matter More than % is measured, more preferably more than 15 mass %.From peel property it is excellent from the viewpoint of be preferably below 70 mass %, more Preferably below 65 mass %, more preferably below 60 mass %.
The weight average molecular weight of above-mentioned (A) binder polymer is preferably 5000~300000, more preferably 10000~ 150000, more preferably 20000~80000, particularly preferably 30000~70000.The viewpoint excellent from resistance to development fluidity is examined It is preferably more than 5000 to consider, more preferably more than 10000, more preferably more than 20000, particularly preferably more than 30000.Separately Outside, from resolution and peel property it is excellent from the viewpoint of be preferably less than 300000, more preferably less than 150000, more Preferably less than 80000, particularly preferably less than 70000.It is explained, the weight average molecular weight and number in present embodiment are divided equally Son amount has been used by gel permeation chromatography (GPC) to determine, value obtained from being converted by polystyrene standard.
The acid number of above-mentioned (A) composition is preferably 50~250mgKOH/g, and more preferably 100~230mgKOH/g is more excellent Elect 130~200mgKOH/g as.From developability it is excellent from the viewpoint of be preferably more than 50mgKOH/g, more preferably More than 100mgKOH/g, more preferably more than 130mgKOH/g.In addition, the resistance to development fluidity from the resist after photocuring It is preferably below 250mgKOH/g, more preferably below 230mgKOH/g from the viewpoint of (adaptation) is excellent, is more preferably Below 200mgKOH/g.
From the viewpoint of cementability and resolution are excellent, the decentralization (Weight-average molecular of above-mentioned (A) binder polymer Amount/number-average molecular weight) it is preferably 1.0~3.0, more preferably 1.0~2.0.
(A) binder polymer may be used alone or in combination two or more to use.Used as by two or more combination In the case of binder polymer, such as the binder polymer of more than two kinds comprising different copolymer compositions, no can be included The same binder polymer of more than two kinds of weight average molecular weight and the binder polymer of more than two kinds of different decentralization. In addition, it is possible to use the polymer with multimode molecular weight distribution that Japanese Unexamined Patent Publication 11-327137 publications are recorded.
It is explained, (A) binder polymer there can be photonasty group as needed.
From film forming, sensitivity and resolution it is excellent from the viewpoint of, the content of (A) composition relative to (A) composition with And the mass parts of total amount 100 of (B) composition are preferably set to 30~70 mass parts, are more preferably set to 35~65 mass parts, more preferably It is set to 40~60 mass parts.
Below, to being illustrated as the photopolymerizable compound of (B) composition.As (B) composition, as long as light can be carried out The material of crosslinking is then not particularly limited, preferably using the compound with ethene unsaturated bond.As with ethene not The compound of saturated bond, can include compound of the intramolecular with 1 ethene unsaturated bond, in intramolecular with 2 The compound of ethene unsaturated bond, there is compound of more than 3 ethene unsaturated bonds etc. in intramolecular.
(B) composition has 2 second containing more than 40 mass % preferably with respect to all quality packs of (B) composition in intramolecular The compound of alkene unsaturated bond, more preferably comprising more than 60 mass %.
As the compound in intramolecular with 2 ethene unsaturated bonds, bisphenol-A system two (methyl) propylene can be included Ester compound, hydrogenated bisphenol A system two (methyl) acrylate compounds, the two (first in intramolecular with amino-formate bond Base) acrylate compounds, in intramolecular there is (poly-) ethylene oxide chain and the poly- alkylene both (poly-) propylene oxide chain Base glycol two (methyl) acrylate compounds, trimethylolpropane two (methyl) acrylate etc..
Among above-mentioned, from the viewpoint of resolution and peel property is improved, (B) composition preferably comprises bisphenol-A system two (methyl) acrylate compounds.
As bisphenol-A system two (methyl) acrylate compounds, the compound represented by following formula (2) can be included.
In formula (2), R3And R4Hydrogen atom or methyl are represented independently of one another.XO and YO represents to aoxidize second independently of one another Alkenyl or oxypropylene group.(XO)ml、(XO)m2、(YO)n1And (YO) n2Independently of one another represent (poly-) ethylene oxide chain or (poly-) propylene oxide chain.ml、m2、n1、n20~40 integer is represented independently of one another.XO is oxyethylene group, YO is oxidation third In the case of alkenyl, ml+m2For 1~40, n1+n2It is m in the case that oxypropylene group, YO are oxyethylene group for 0~20, XOl +m2For 0~20, n1+n2For 1~40.It is explained, the polymerization methodses of (poly-) ethylene oxide chain or (poly-) propylene oxide chain can be with To be random, or block.From the viewpoint of more resolution and adaptation is improved, by the compound of formula (2) expression Among, preferably and use ml+m2For 1~6, n1+n2Compound and, m for 0l+m2For 8~40, n1+n2For 0~20 compound and Use.
Among the compound represented by formula (2), 2,2- double (4- (methacryloxy diethoxy) phenyl) propane) can Commercially obtained as BPE-200 (Xin Zhong villages chemical industry (strain) is made, trade name), 2,2- double (4- (methacryloxies Five ethyoxyls) phenyl) propane can be used as BPE-500 (Xin Zhong villages chemical industry (strain) make, trade name) or FA-321M (Hitachis Into industrial (strain) system, trade name) commercially obtain, 2,2- double (4- (ethyoxyl of methacryloxy 15) phenyl) propane BPE-1300 (Xin Zhong villages chemical industry (strain) is made, trade name) can be used as commercially to obtain.They can be used alone or arbitrarily Combine two or more and use.
In addition, from the viewpoint of the flexibility of solidfied material (cured film) for improving photosensitive polymer combination, (B) composition is excellent Choosing includes PAG two (methyl) acrylate.As the content of PAG two (methyl) acrylate, phase It is preferably 3~70 mass % for all quality of (B) composition, more preferably 5~60 mass %.
As PAG two (methyl) acrylate, preferably intramolecular have (poly-) ethylene oxide chain and PAG two (methyl) acrylate of both (poly-) propylene oxide chains.In PAG two (methyl) propylene The intramolecular of acid esters, (poly-) ethylene oxide chain and (poly-) propylene oxide chain continuously can exist block respectively, also can nothing Rule ground is present.It is explained, the oxypropylene group in (poly-) propylene oxide chain can be the positive propylidene of oxo or oxo different sub- third Any one in base.In addition, in (poly-) oxidation isopropyl alkene chain, the secondary carbon of propylidene can be combined in oxygen atom, and primary carbon can also combine In oxygen atom.
PAG two (methyl) acrylate further can also have as (poly-) oxidation n-butene chain, (poly-) oxygen Change the carbon number 4~6 of isobutene chain, (poly-) oxidation n-pentene chain, (poly-) oxidation hexene chain or their constitutional isomer etc. (poly-) oxyalkylene chain of left and right.
As PAG two (methyl) acrylate, the change particularly preferably represented by following formula (3), (4) or (5) Compound.They, which may be used alone or in combination, uses two or more.
In formula (3), (4) and (5), R5~R10Hydrogen atom or methyl are represented independently of one another, and EO represents oxyethylene group, PO Represent oxypropylene group.r1、r2、r3And r4Represent the repeat number of construction unit formed by oxyethylene group, s1、s2、s3And s4 Represent the repeat number of construction unit formed by oxypropylene group, the repetition sum r of oxyethylene group1+r2、r3And r4It is (average Value) independently of one another represent 1~30 integer, the repetition sum s of oxypropylene group1、s2+s3And s4(average value) is each only On the spot represent 1~30 integer.
In the compound represented by formula (3), (4) or (5), the repetition sum r of oxyethylene group1+r2、r3And r4For 1~30 Integer, preferably 1~10 integer, more preferably 4~9 integer, more preferably 5~8 integer.The sum of the repeat number During more than 30, then the tendency for being difficult to obtain sufficient resolution, adaptation and resist shape is there are.
In addition, the repetition sum s of oxypropylene group1、s2+s3And s4For 1~30 integer, preferably 5~20 it is whole Number, more preferably 8~16 integer, more preferably 10~14 integer.When the sum of the repeat number is more than 30, then exist in distress To obtain sufficient resolution, the tendency of sludge is easily produced.
As the compound represented by formula (3), R can be included5And R6=methyl, r1+r2=6 (average values), s1=12 is (flat Average) vinyl compound (Hitachi Chemical Industries (Ltd.) system, trade name " FA-023M ") etc..As the change represented by formula (4) Compound, R can be included7And R8=methyl, r3=6 (average values), s2+s3Vinyl compound (the Hitachi of=12 (average values) Into industrial (strain) system, trade name " FA-024M ") etc..As the compound represented by formula (5), R can be included9And R10=hydrogen is former Son, r4=1 (average value), s4The vinyl compound of=9 (average values) (make, sample name " NK by Xin Zhong villages chemical industry (strain) ESTER HEMA-9P (NK エ ス テ Le HEMA-9P) ") etc..They, which may be used alone or in combination, uses two or more.
(B) in the case that composition is included in the photopolymerizable compound that intramolecular has 1 ethene unsaturated bond, from flat From the viewpoint of weighing apparatus improves the peel property after resolution, adaptation, resist shape and solidification well, its content is relative In all quality of (B) composition be preferably 1~30 mass %, more preferably 3~25 mass %, more preferably 5~20 matter Measure %.
As the compound in intramolecular with 1 ethene unsaturated bond, nonylphenoxy polyethylene oxygen can be included Base acrylate (ノ ニ Le Off ェ ノ キ シ Port リ エ チ レ Application オ キ シ ア Network リ レ ー ト), phthalic acid based compound (Off タ Le acid based compound), (methyl) alkyl acrylate etc..
Among above-mentioned, the peel property after resolution, adaptation, resist shape and solidification is improved well from balance From the viewpoint of, (B) composition preferably comprises nonylphenoxy polyethylene epoxide acrylate or phthalic acid based compound.
As above-mentioned nonylphenoxy polyethylene epoxide acrylate, Nonylphenoxy triethylene epoxide propylene can be included Acid esters, the ethyleneoxy acrylate of Nonylphenoxy four, the ethyleneoxy acrylate of Nonylphenoxy five, the second of Nonylphenoxy six Alkenyloxy group acrylate, the ethyleneoxy acrylate of Nonylphenoxy seven, the ethyleneoxy acrylate of Nonylphenoxy eight, nonyl The ethyleneoxy acrylate of phenoxy group nine, the ethyleneoxy acrylate of Nonylphenoxy ten, the ethyleneoxy of Nonylphenoxy 11 Acrylate etc..They can be used alone or are combined two or more and use.It is explained, " nonylphenoxy polyethylene oxygen Base acrylate " is also referred to as " Nonylphenoxy polyethylene glycol acrylate ".
Among them, the ethyleneoxy acrylate of Nonylphenoxy eight for example can be used as M-114 (East Asia synthesis (strain) system, Trade name, the ethyleneoxy acrylate of 4- n-nonyls phenoxy group eight) commercially obtain.It is explained, " 4- n-nonyl phenoxy groups Eight ethyleneoxy acrylate " are also referred to as " ethylene glycol acrylate of 4- n-nonyls phenoxy group eight ".
As above-mentioned phthalic acid based compound, such as γ-chloro- beta-hydroxy propyl group-β '-(methyl) acryloyl can be included Epoxide ethyl-phthalic acid ester, beta-hydroxy ethyl-β '-(methyl) acryloyl-oxyethyl-phthalic acid ester and β-hydroxyl Base propyl group-β '-(methyl) acryloyl-oxyethyl-phthalic acid ester, wherein, preferably γ-chloro- beta-hydroxy propyl group-β '-(first Base) acryloyl-oxyethyl-phthalic acid ester.γ-adjacent the benzene two of chloro- beta-hydroxy propyl group-β '-methacryloxyethyls- Formic acid esters can commercially obtain as FA-MECH (Hitachi Chemical Industries (Ltd.) system, trade name).They can be used alone or group Conjunction uses two or more.
Being included in intramolecular in (B) composition has a case that the photopolymerizable compound of more than 3 ethene unsaturated bonds Under, from the viewpoint of improving the peel property after resolution, adaptation, resist shape and solidification well from balance, its Content is preferably 5~50 mass % relative to all quality of (B) composition, more preferably 10~40 mass %.
As the compound in intramolecular with more than 3 ethene unsaturated bonds, trimethylolpropane tris can be included (methyl) acrylate, EO be modified trimethylolpropane tris (methyl) acrylate (the repetition sum of oxyethylene group for 1~ 5), PO is modified trimethylolpropane tris (methyl) acrylate, EO, PO are modified trimethylolpropane tris (methyl) acrylate, Tetramethylol methane three (methyl) acrylate, tetramethylol methane four (methyl) acrylate, dipentaerythritol five (methyl) Acrylate, dipentaerythritol six (methyl) acrylate etc..They, which may be used alone or in combination, uses two or more.They it In, as retrievable material, can including A-TMM-3, (Xin Zhong villages chemical industry (strain) is made, trade name, tetramethylol methane Triacrylate), TMPT21E, TMPT30E (Hitachi Chemical Industries (Ltd.) system, sample name, EO be modified trimethylolpropane tris first Base acrylate) etc..
(B) all contents of composition be preferably set to 30 relative to the mass parts of total amount 100 of (A) composition and (B) composition~ 70 mass parts, are more preferably set to 35~65 mass parts, are more preferably set to 35~60 mass parts.It is excellent from sensitivity and resolution From the viewpoint of different be preferably 30 mass parts more than, from resist shape it is excellent from the viewpoint of be preferably 70 mass parts below.
Below, (C) Photoepolymerizationinitiater initiater is illustrated.The photosensitive polymer combination of the present invention is characterised by, is wrapped (C) Photoepolymerizationinitiater initiater is used as containing the compound represented by following formula (1).
In formula (1), R1And R2The group shown in following formula (1a) or (1b) is represented independently of one another.
In formula (1a) and (1b), R represents the alkyl or phenyl of carbon number 1~20 independently of one another, from the sight of reactivity Point consideration, the preferably alkyl of the alkyl or phenyl of carbon number 1~3, more preferably carbon number 1~3.Multiple R Can be with identical also different.
The compound represented by above-mentioned formula (1) can be represented by following formula (1c).
In above-mentioned formula (1c), X represents S (sulphur atom) or without bonding (be not bonded and do not form ring) independently of one another.Separately Outside, R represents the alkyl or phenyl of carbon number 1~20 independently of one another, from the viewpoint of reactivity, preferably carbon number The alkyl of 1~3 alkyl or phenyl, more preferably carbon number 1~3.
In the range of the maximum absorption wavelength of the compound represented by above-mentioned formula (1) is preferably 350~410nm.Thus, it is right Good sensitivity, while the absorption at the long wavelength side more than wavelength 500nm can be obtained in 350~410nm of wavelength light Tail off, the stability under gold-tinted becomes good.
By above-mentioned formula (1) represent compound content relative to (A) composition and (B) composition the mass parts of total amount 100 0.01~3 mass parts are preferably set to, are more preferably set to 0.05~2 mass parts, are more preferably set to 0.05~1 mass parts, especially It is preferably set to 0.05~0.5 mass parts.By using the compound represented by above-mentioned formula (1), even relative to (A) composition with And the content that the mass parts of total amount 100 of (B) composition are 0.01~0.5 mass parts, the also direct description exposure to wavelength 405nm are High sensitivity, resolution and adaptation can be improved.
(C) composition can be also included beyond the compound represented by formula (1) with not damaging the degree of effect of the present invention Other Photoepolymerizationinitiater initiaters.As other Photoepolymerizationinitiater initiaters, such as benzophenone, 2- benzyl -2- diformazans can be included Base amino -1- (4- morphlinophenyls)-butanone -1,2- methyl isophthalic acid-[4- (methyl mercapto) phenyl] -2- morpholinoes (モ Le Off ォ リ ノ)-benzil derivatives such as the grade aromatic ketone of acetone -1, benzil dimethyl ketal, 2- (Chloro-O-Phenyl) -4,5- diphenyl miaows 2,4, the 5- triarylimidazoles dimers such as azoles dimer, 2- (o-fluorophenyl) -4,5- diphenyl-imidazole dimers, 9- phenyl a word used for translations The acridine derivatives such as pyridine, 1,7- (9,9 '-acridinyl) heptane, and acylphosphine oxide derivative.They can be used alone or group Two or more is closed to use.
(C) content of composition is preferably set to 0.01~10 relative to the mass parts of total amount 100 of (A) composition and (B) composition Mass parts, are more preferably set to 0.05~5 mass parts, are more preferably set to 0.1~3 mass parts.It there are following tendency：(C) into Point content to be more than 0.01 mass parts when be then readily available good sensitivity and resolution, then hold when below 10 mass parts Easily obtain good shape.
In addition, in the photosensitive polymer combination of present embodiment, also can be further for the purpose of more improving sensitivity Include (D) sensitizing coloring matter and/or (E) hydrogen supply compound.
As (D) sensitizing coloring matter, such as dialkyl amido benzophenone cpd, pyrazoline compounds, anthracene can be included Compound, coumarin compound, xanthone compound, oxazole compounds, benzoazole compounds, thiazolium compounds, benzo Thiazolium compounds, triazole compounds, stilbene compounds, triaizine compounds, thiophene compound, naphthalimide compounds and three Amines.They may be used alone or in combination two or more to use.
(D) content of sensitizing coloring matter is preferably set to 0.01 relative to the mass parts of total amount 100 of (A) composition and (B) composition ~10 mass parts, are more preferably set to 0.05~5 mass parts, are more preferably set to 0.1~2 mass parts.It there are following tendency：Should Then easily improve sensitivity and resolution when use level is more than 0.01 mass parts, be then readily available when below 10 mass parts good Good shape.Can individually using or combine two or more to use.
As (E) hydrogen supply compound, such as double [4- (dimethylamino) phenyl] methane, double [4- (diethyls can be included Base amino) phenyl] methane, leuco crystal violet and N-phenylglycine.
(E) content of hydrogen donor compound is preferably set to relative to the mass parts of total amount 100 of (A) composition and (B) composition 0.01~10 mass parts, are more preferably set to 0.05~5 mass parts, are more preferably set to 0.1~2 mass parts.They can be single respectively Solely two or more is used or combined to use.
The photosensitive polymer combination of present embodiment, also can as needed and containing intramolecular have it is at least one can Carry out the photopolymerizable compound (oxetane compound etc.) of the cyclic ether group of cationic polymerization, cationic polymerization triggers The plasticising such as the light colour formers such as the dyestuffs such as agent, peacock green, tribromo-benzene sulfone, leuco crystal violet, heat colour developing preventing agent, para toluene sulfonamide Agent, pigment, filler, defoamer, fire retardant, stabilizer, adaptation imparting agent, levelling agent, peel off accelerator, antioxidant, Spices, preparation, thermal cross-linking agent etc..They may be used alone or in combination two or more to use.Their content is relative to (A) The mass parts of total amount 100 of composition (binder polymer) and (B) composition (photopolymerizable compound), it is preferably set to 0.01 respectively~ 20 mass parts or so.
(solution of photosensitive polymer combination)
The photosensitive polymer combination of present embodiment can be dissolved in organic solvent, so as to be used as solid constituent 30~60 The solution (coating fluid) of quality % or so photosensitive polymer combination uses.As organic solvent, such as first can be included Alcohol, ethanol, acetone, MEK, methyl cellosolve, ethyl cellosolve, toluene, N,N-dimethylformamide, propylene glycol monomethyl ether Or their mixed solvent.
By above-mentioned coating solution on the surface of metallic plate etc., it is dried, so as to be formed by present embodiment The photosensitive polymer combination layer that photosensitive polymer combination is formed.As metallic plate, can enumerate copper, copper series alloy, nickel, The iron-based alloys such as chromium, iron and stainless steel, it can preferably enumerate copper, copper series alloy and iron-based alloy.
The thickness of photosensitive polymer combination layer is different because of its purposes, is preferably calculated as 1~100 μm with dried thickness Left and right.The surface of the side opposite with metallic plate side of photosensitive polymer combination layer can be also coated to by diaphragm.As guarantor Cuticula, polymer films such as polyethylene, polypropylene etc. can be included.
Not only sensitivity, resolution and excellent adhesion but also the plating of the photosensitive polymer combination layer of present embodiment Cover that the peel property of the resist after formative and plating is excellent, play the low such effect of contaminative for plating.
(photosensitive element)
Below, the photosensitive polymer combination layer and photosensitive element of present embodiment are illustrated.Fig. 1 is expression The pattern sectional view of one example of photosensitive element.Photosensitive element 1 is, by support membrane 2, photosensitive polymer combination layer 3, And diaphragm 4 optionally is according to layered product obtained from this order stacking.
By the solution coating of above-mentioned photosensitive polymer combination on support membrane 2, it is dried, so as in support membrane 2 It is upper to form the photosensitive polymer combination layer 3 formed by above-mentioned photosensitive polymer combination.By so operating, can be possessed The photonasty member of the present embodiment of support membrane 2 and the above-mentioned photosensitive polymer combination layer 3 formed on the support membrane 2 Part.
As support membrane 2, polyester, polypropylene, the polyethylene such as polyethylene terephthalate etc. can be used to have heat-resisting The polymer film of property and solvent resistance.The thickness of support membrane (polymer film) is preferably 1~100 μm, more preferably 5~50 μ M, more preferably 5~30 μm.
Coating of the solution of photosensitive polymer combination on support membrane 2 can be coated with (comma by roller coat, unfilled corner wheel Coat), intaglio plate coating, airblade coating, die coating, scrape the known methods such as rod coating to carry out.
The drying of the solution of photosensitive polymer combination is carried out 5~30 minutes or so preferably at 70~150 DEG C.Dry Afterwards, the remaining organic solvent amount in photosensitive polymer combination layer 3 from prevent in process below occur organic solvent diffusion From the viewpoint of be preferably set to below 2 mass %.
The thickness of photosensitive polymer combination layer 3 in photosensitive element 1 is different because of purposes, preferably with dried thickness Degree is calculated as 1~100 μm, more preferably 1~50 μm, more preferably 5~50 μm, particularly preferably 10~40 μm.In the presence of just like Lower tendency：When the thickness is more than 1 μm, then easy industrialness it is coated with, at less than 100 μm, is then readily available sufficient closely sealed Property and resolution.
The ultraviolet of transmissivity on to(for) photosensitive polymer combination layer 3, for wavelength 405nm ultraviolet, preferably For 5~75%, more preferably 10~65%, more preferably 15~55%.It there are following tendency：The transmissivity be 5% with When upper, then sufficient adaptation was readily available, when less than 75%, be then readily available sufficient resolution.Above-mentioned transmissivity can lead to UV spectrometers are crossed to determine.As UV spectrometers, Hitachi 228A type W beam spectrophotometers etc. can be included.
Photosensitive element 1 can also possess the opposite with the side of support membrane 2 of photosensitive polymer combination layer 3 as needed The surface of side carries out coated diaphragm 4.
As diaphragm 4, preferably it is less than support membrane 2 for photosensitive for the bonding force of photosensitive polymer combination layer 3 The bonding force of property resin composition layer, it is additionally preferred to the film of low flake.Herein, " flake " refers to, melts by material hot melt, passes through Be kneaded, extrusion, biaxial stretch-formed, casting process (casting method) etc. and when manufacturing film, the foreign matter of material, non-liquefactent, oxygen Change the situation that degraded matter etc. is incorporated into film.That is, " low flake " refers to that above-mentioned foreign matter in film etc. is few.
Specifically, as diaphragm 4, polyester, polypropylene, the polyethylene such as polyethylene terephthalate etc. can be used Polymer film with heat resistance and solvent resistance.As commercially available product, the Alphan (ア that Oji Paper (strain) is made can be included Le Off ァ Application) MA-410, E-200C, SHIN-ETSU HANTOTAI Film (strain) systems etc. polypropylene screen, the poly- second such as NF-15 of TAMAPOLY (strain) systems The polyethylene terephthalate film of the PS series such as alkene film, the PS-25 of Supreme Being people's (strain) system etc..It is explained, diaphragm 4 also may be used To be and support membrane identical film.
The thickness of diaphragm 4 is preferably 1~100 μm, more preferably 5~50 μm, more preferably 5~30 μm, especially excellent Elect 15~30 μm as.When the thickness is more than 1 μm, then (lamination) photosensitive polymer combination layer 2 is laminated on substrate and is protected During cuticula 4, diaphragm 4 is not easily broken, and from the viewpoint of cheapness is then good at less than 100 μm.
Photosensitive element also can further have the intermediate layer of cushion, adhesive linkage, light absorbing layer, gas-barrier layer etc. Deng.
The photosensitive element 1 obtained can sheet keeping or web-like batch in core and take care of.Roll up web-like In the case of taking, preferably batched in the way of support membrane 2 turns into outside.As core, polyvinyl resin, poly- third can be included The plastics such as olefine resin, polystyrene resin, Corvic, ABS resin (acrylonitrile-butadiene-styrene copolymer). On the end face of photosensitive element by so operating the web-like to obtain, end face is preferably provided with from the viewpoint of being protected from end face Isolator, damp proof end face isolator is preferably provided with from the viewpoint of the welding of resistance to edge.As bundling method, preferably wrap into saturating Moist small black sheet and pack.
(forming method of resist pattern)
Using above-mentioned photosensitive polymer combination, resist pattern can be formed.The formation side of the resist pattern of present embodiment Method has following process：(i) the photosensitive polymer combination layer formed by above-mentioned photosensitive polymer combination is laminated on substrate Lamination process, (ii) active ray is irradiated to the established part of photosensitive polymer combination layer and make established part exposure, The exposure process of solidification, and (iii) remove the part beyond the above-mentioned established part of photosensitive polymer combination layer from substrate, So as to form the developing procedure of the resist pattern formed by the solidfied material of photosensitive polymer combination on substrate.
(i) lamination process
First, the photosensitive polymer combination formed by photosensitive polymer combination is laminated on substrate layer by layer.As base Plate, the substrate (circuit formation substrate) for possessing the conductor layer for having insulating barrier and being formed on which insulating layer can be used.
Stacking of the photosensitive polymer combination layer on substrate is for example carried out by the following method：By above-mentioned photosensitive element Diaphragm remove, then on one side by the heating of the photosensitive polymer combination layer of photosensitive element while being crimped on aforesaid substrate. Thus, can obtain comprising substrate, photosensitive polymer combination layer and support membrane, and the layered product of their stacked above one another.
From the viewpoint of adaptation and followability, the stacking operation is preferably carried out under reduced pressure.It is photosensitive during crimping Property resin composition layer and/or the heating of substrate preferably carried out at a temperature of 70~130 DEG C, it is preferably left in 0.1~1.0MPa The right side (1~10kgf/cm2Left and right) pressure under crimp, but these conditions are not particularly limited.It is explained, if will be photosensitive Property resin composition layer be heated to 70~130 DEG C, then the pre-heat treatment and nonessential is carried out to substrate in advance, but in order to further Stackability is improved, can also carry out the pre-heat treatment of substrate.
(ii) exposure process
Then, active ray is irradiated to the established part of the photosensitive polymer combination layer on substrate and makes the established part Exposure, solidification.Now, in the case of support membrane present on photosensitive polymer combination layer is radioparent for active ray, Active ray can be irradiated by support membrane, but in the case that support membrane is light-proofness, to photosensitive after support membrane is removed Property resin composition layer irradiation active ray.
As exposure method, can include by the negative or positive mask pattern for being referred to as wiring diagram (artwork) and image shape Ground irradiates the method (mask exposure method) of active ray.Exposed in addition, can also use by LDI (Laser Direct Imaging) Light method, DLP (Digital Light Processing) exposure method etc. irradiate active light with directly describing exposure method and image shape The method of line.
As the light source of active ray, known light source can be used, such as carbon arc lamp, mercury-vapor arcs, height can be used The solid state lasers such as the gas lasers such as medium pressure mercury lamp, xenon lamp, argon gas laser, YAG laser, semiconductor laser etc. have The light source of effect ground radiation ultraviolet or visible ray.
It is excellent from the viewpoint of the effect for more reliably obtaining the present invention as the wavelength (exposure wavelength) of active ray Choosing is set in the range of 350~420nm.
The photosensitive polymer combination of present embodiment, which can be suitably used in, directly describes exposure method.That is, it is of the invention One of preferred embodiment be application of the photosensitive polymer combination in exposure method is directly described, the photosensitive resin composition Thing contains (A) binder polymer, (B) photopolymerizable compound, (C) Photoepolymerizationinitiater initiater, above-mentioned (C) Photoepolymerizationinitiater initiater bag Containing the compound represented by above-mentioned formula (1).
(iii) developing procedure
Further, the part beyond the above-mentioned established part of photosensitive polymer combination layer is removed from substrate, so that The resist pattern formed by the solidfied material of photosensitive polymer combination is formed on substrate.Exist on photosensitive polymer combination layer In the case of Supported film, after removing support membrane, part (the unexposed portion beyond above-mentioned established part (exposed portion) is carried out Point) removal (development).There are wet development and dry process development in developing method, but be widely used for wet development.
In the case of based on wet development, using the developer solution corresponding to photosensitive polymer combination, by known aobvious Image method develops.As developing method, include and used impregnation method, sheathed submergence mode (バ ト Le mode), spraying square Formula, brushing, slap (ス ラ ッ ピ Application グ), blade coating (ス Network ラ ッ ピ Application グ), the method for shaking impregnating, are improved from resolution Viewpoint considers most preferably high-pressure fog mode.Also these methods of more than two kinds can be combined and is developed.
As developer solution, alkaline aqueous solution, water system developer solution, organic solvent system developer solution etc. can be included.
Safe and stable in the case that alkaline aqueous solution is used as developer solution, operability is good.As alkaline aqueous solution Alkali, can be used the alkali hydroxide such as hydroxide of lithium, sodium or potassium, the carbonic acid such as lithium, sodium, potassium or the carbonate of ammonium or bicarbonate Alkali metal pyrophosphates such as the alkali metal phosphate such as alkali, potassium phosphate, sodium phosphate, sodium pyrophosphate, potassium pyrophosphate etc..
As alkaline aqueous solution, preferably the weak solution of 0.1~5 mass % sodium carbonate, 0.1~5 mass % potassium carbonate it is dilute Solution, the weak solution of 0.1~5 mass % sodium hydroxides, weak solution of 0.1~5 mass % sodium tetraborates etc..Alkaline aqueous solution PH is preferably set to 9~11 scope, and its temperature is adjusted according to the alkali-developable of photosensitive polymer combination layer.It is water-soluble in alkalescence , also can mixed surfactant, defoamer, a small amount of organic solvent etc. for promoting development in liquid.
Water system developer solution is, for example, to include water or the developer solution of alkaline aqueous solution and more than a kind of organic solvent.Herein, make For the alkali of alkaline aqueous solution, in addition to foregoing material, such as borax, sodium metasilicate (メ タ ケ イ acid Na ト are also listed out リ ウ system), TMAH, monoethanolamine, ethylenediamine, diethylenetriamines, 2- amino -2- hydroxymethyls -1,3- the third two Alcohol, 1,3- diamino-propanols -2 and morpholine.The pH of water system developer solution preferably reduces as far as possible in the scope fully developed, It is preferably set to pH8~12, more preferably be set to pH9~10.
As the organic solvent for water system developer solution, acetone, ethyl acetate can be included, there is carbon number 1~4 Alkoxyethanol, ethanol, isopropanol, butanol, diethylene glycol monomethyl ether, TC, the diethyl two of alkoxy Alcohol single-butyl ether etc..They may be used alone or in combination two or more to use.The concentration of organic solvent in water system developer solution is led to 2~90 mass % often are preferably set to, its temperature can adjust according to alkali-developable.Also surface can be mixed into water system developer solution on a small quantity Activating agent, defoamer etc..
As organic solvent system developer solution, 1,1,1- trichloroethanes, 1-METHYLPYRROLIDONE, N, N- dimethyl methyls are included The organic solvents such as acid amides, cyclohexanone, methyl iso-butyl ketone (MIBK), gamma-butyrolacton.It is excellent in order to prevent igniting in these organic solvents It is selected in 1~20 mass % scope addition water.
After removing unexposed portion, 60~250 DEG C or so of heating or 0.2~10J/cm can be also carried out as needed2It is left Right exposure, further solidifies resist pattern.
(manufacture method of printed circuit board (PCB))
By to be etched by the above method and the substrate formed with resist pattern or plating, so as to manufacture printing Circuit board.The etching or plating of substrate, as mask, are directed to conductor layer of substrate etc. and carried out coated with the resist pattern formed.
Etching solution in the case of as being etched, it is molten that copper chloride solution, ferric chloride solution, alkaline etching can be included Liquid, hydrogen peroxide etching solution, among them, from etching factor (etch factor) it is good from the viewpoint of preferably use chlorine Change ferrous solution.
As the coating method in the case of progress plating, the plating of the copper such as copper sulphate plating, cupric pyrophosphate plating can be included Cover, the solder plating such as high uniformity (Ha イ ス ロ ー) solder plating, watt bath (nickel sulfate-nickel chloride) plating, sulfamic acid The nickel plating such as nickel, hard golden plating (ハ ー De gold メ ッ キ), the golden plating such as soft golden plating (ソ Off ト gold メ ッ キ).
After etching or plating terminate, resist pattern can for example pass through the alkalescence water more stronger than the alkaline aqueous solution for developing Solution is peeled off.As the aqueous solution of the strong basicity, such as 1~10 mass % sodium hydrate aqueous solutions, 1~10 matter can be used Measure % potassium hydroxide aqueous solutions or amine stripper.Wherein preferred amines stripper.
As the stripping mode of resist pattern, submergence mode, spray pattern etc. can be included, they, which can be used alone, also may be used It is used in combination.In addition, the printed circuit board (PCB) formed with resist pattern can be multilayer board, can also have path through hole.
The photosensitive polymer combination of present embodiment suitably can be used in the manufacture of printed circuit board (PCB).That is, this hair One of bright preferred embodiment is the application of photosensitive polymer combination in the manufacturing of printed circuit boards, the photoresist Composition contains (A) binder polymer, (B) photopolymerizable compound and (C) Photoepolymerizationinitiater initiater, and above-mentioned (C) photopolymerization is drawn Send out agent and include the compound represented by above-mentioned formula (1).
More than, the preferred embodiment of the present invention is illustrated, but the present invention is not by any of above-mentioned embodiment Limit.
[embodiment]
Embodiment is exemplified below out more specifically to illustrate the present invention.But the present invention is not only restricted to following implementation Example.
(embodiment 1~10 and comparative example 1~3)
(preparation of the solution of photosensitive polymer combination)
Composition shown in table 1 below is mixed with the use level shown in the table, so as to be prepared for embodiment 1~10 and ratio Compared with the solution of the photosensitive polymer combination of example 1~3.It is explained, the use level of (A) composition shown in table 1 and table 2 is not wave Send out the quality (solid constituent amount) of composition.The details of each composition shown in table 1 below and 2 is as described below.
＜ (A) binder polymers ＞
[synthesis of binder polymer (A-1)]
Will be as the methacrylic acid 150g, benzyl methacrylate 125g, metering system of polymerizable monomer (monomer) The solution that sour methyl esters 25g and styrene 200g (mass ratio 30/25/5/40) mix and obtained with, azodiisobutyronitrile 9.0g It is set to " solution a ".
By to methyl cellosolve 60g and toluene 40g mixed liquor (mass ratio 3：2) azodiisobutyronitrile is dissolved in 100g 1.2g and the solution that obtains is set to " solution b ".
To possess have mixer, reflux condenser, thermometer, dropping funel and nitrogen ingress pipe flask in, input Methyl cellosolve 270g and toluene 180g mixed liquor (mass ratio 3：2) 450g, while being blown into nitrogen into flask while stirring Mix, be heated to 80 DEG C.
After above-mentioned solution a was added dropwise through 4 hours in above-mentioned mixed liquor into flask, stir while being incubated at 80 DEG C 2 hours.Then, in the solution into flask after 10 minutes are added dropwise above-mentioned solution b, stir solution in flask while 3 hours are incubated at 80 DEG C.Further, the solution in flask is warming up to 90 DEG C through 30 minutes, 2 hours is incubated at 90 DEG C, Then cooled down and obtain binder polymer (A-1) solution.
The nonvolatile component (solid constituent) of binder polymer (A-1) is 47.8 mass %, and weight average molecular weight is 30000, acid number 196mgKOH/g.It is explained, weight average molecular weight is determined by gel permeation chromatography (GPC), is used The standard curve of polystyrene standard and convert so as to export.GPC condition is as shown below.
(GPC conditions)
Pump：Hitachi's L-6000 types [(strain) Hitachi system]
Chromatographic column：Gelpack GL-R420+Gelpack GL-R430+Gelpack GL-R440 (meter 3) (more than, day Vertical chemical conversion industry (strain) system, trade name)
Elutriant：Tetrahydrofuran
Measurement temperature：40℃
Flow：2.05mL/ minute
Detector：Hitachi L-3300 types RI ((strain) Hitachi system)
＜ (B) photopolymerizable compounds ＞
TMPT21E：Trimethylolpropane polyethylene glycol oxide ether trimethyl acrylic ester (Hitachi Chemical Industries (Ltd.), commodity Name)
FA-321M：Double (4- (ethyoxyl of the methacryloxy five) phenyl) propane of 2,2-) (Hitachi Chemical Industries (Ltd.) System, trade name)
FA-024M：R in the compound represented by above-mentioned formula (4)7And R8=methyl, r3=6 (average values), s2+s3=12 The compound (Hitachi Chemical Industries (Ltd.) system, trade name) of (average value)
BPE-200：Double (4- (the poly- diethoxy of the methacryloxy) phenyl) propane of 2,2-) (the ring contained by 1 molecule Oxidative ethane chain is 4 moles) (Xin Zhong villages chemistry (strain) system, trade name)
M-114：The ethylene glycol acrylate of 4- n-nonyls phenoxy group eight (East Asia synthesis (strain) system, trade name)
＜ Photoepolymerizationinitiater initiaters (C) ＞
[Photoepolymerizationinitiater initiater (C-1)：OXE-TPABP synthesis]
Sodium hydride 4.14g (0.17mol) and dry DMF 150mL is added into flask, in a nitrogen atmosphere at room temperature Stirring 30 minutes, diphenylamine 33.98g (0.20mol) is then added, then, add double (4- fluorophenyls) ketone 15.27g (0.07mol), stirred 12 hours at 150 DEG C.Thereafter reaction solution is injected water into, the reaction product with filtered off with suction.Use second Alcohol is recrystallized, and obtains the solid A of yellow.
Then, in a nitrogen atmosphere, to adding aluminium chloride 13.87g (20mmol), chloroacetic chloride in 200mL flasks In 2.95mL (41.6mmol) and dichloromethane 60mL solution, while being cooled down by ice bath, while being added dropwise by dichloromethane 40mL dissolves solution obtained from obtained solid A4.2g (8mmol).After completion of dropwise addition, it is small to continue reaction 1 in ice bath When, continue reaction 7 hours under air, reactant is flow into frozen water, organic layer has been taken out with separatory funnel.To have with water Machine layer carry out 3 times washing, with Rotary Evaporators by solvent distillation remove after, with vacuum drier (60 DEG C) carries out a night drying and Obtain product B.
Product B 1.0g (1.5mmol) are dissolved with DMA 30mL, add hydroxylamine hydrochloride 0.834g (12mmol) and sodium acetate 1.132g (13.8mmol), stirred 7 hours at 100 DEG C.Then, reactant is injected into water, Sediment is isolated with filtering, is then dried with vacuum drier and obtains product C.
Into the solution obtained from lysate C in the solution 40mL of chloroform/dichloromethane=1/1, dripped through 30 minutes Add acetic anhydride 1.0mL (10.8mmol), reacted thereafter 7 hours.Reaction solution is entered with 5 mass % sodium hydrate aqueous solutions 5mL Row neutralizes, and carries out 3 washings with water, is dried organic layer with anhydrous magnesium sulfate.Then, organic layer is separated by filtration, with rotation Evaporimeter, which distills solvent, to be removed, and is then recrystallized with ethanol, obtains purpose product (C-1)：OXE-TPABP.
By the 1H-NMR spectrograms shown in Fig. 2, it is the chemical combination with the structure represented by following formula to confirm product (C-1) Thing.
[Photoepolymerizationinitiater initiater (C-2)：OXE-TPSBP synthesis]
In above-mentioned Photoepolymerizationinitiater initiater (C-1) synthesis, diphenylamine is substituted using phenthazine, in addition, with (C-1) synthesis similarly operates, and obtains the compound (C-2) with the structure represented by following formula.
[synthesis of Photoepolymerizationinitiater initiater (C-3)]
In above-mentioned Photoepolymerizationinitiater initiater (C-1) synthesis, double (4- fluorophenyls) first are substituted using 4- fluorine benzophenone Ketone, in addition, operated in the same manner as the synthesis with (C-1), obtain the compound (C- with the structure represented by following formula 3)。
[synthesis of Photoepolymerizationinitiater initiater (C-4)]
In above-mentioned Photoepolymerizationinitiater initiater (C-1) synthesis, double (4- fluorophenyls) first are substituted using 4- fluorine benzophenone Ketone, diphenylamine is substituted using phenthazine, in addition, operated in the same manner as the synthesis with (C-1), obtained with by following The compound (C-4) for the structure that formula represents.
[other Photoepolymerizationinitiater initiaters]
BCIM：2,2 '-bis- (2- chlorphenyls) -4,4 ', 5,5 '-tetraphenyl double imidazole (Hampford company systems, trade name)
＜ (D) sensitizing coloring matters ＞
Nikkafluor(ニッカフロー)MC：((strain) Japan Chemical Industry is made：7- diethylamino -4- methyl is fragrant Legumin)
＜ (E) hydrogen supply compound ＞
LCV：Leuco crystal violet (hillside plot chemistry (strain) system, trade name)
MBO：2- mercaptobenzoxazoles
NPG：N-phenylglycine
Table 1
Table 2
(photosensitive element)
The solution of above-mentioned photosensitive polymer combination is equably coated on to the poly terephthalic acid second of 16 μm of thickness respectively On diol ester film (Supreme Being people's (strain) makes, trade name " HTF-01 "), dried with 70 DEG C and 110 DEG C of hot wind convection type driers, So as to form the photosensitive polymer combination layer that dried thickness is 40 μm.It is bonded on the photosensitive polymer combination layer Diaphragm (TAMAPOLY (strain) makes, trade name " NF-15 "), obtains polyethylene terephthalate film (support membrane), sense Photosensitive element obtained from photosensitive resin composition layer and diaphragm stacked above one another.
(multilayer board)
For covering comprising glass epoxy resin (glass-epoxy) material and copper foil (35 μm of the thickness) that is formed at its two sides The copper surface of layers of copper lamination (Hitachi Chemical Industries (Ltd.) system, trade name " MCL-E-67 "), using with the brush equivalent to #600 The grinder (three Kei (strain) system) of son is ground, washed, and is then dried with air stream.By the copper-clad laminated board (hereinafter referred to as " substrate ".) heat and be warming up to 80 DEG C, the photosensitive element of embodiment 1~10 and comparative example 1~3 is then laminated (stacking) In the copper surface of substrate.On lamination, while diaphragm is removed, while in 120 DEG C of temperature, lamination pressure 4kgf/cm2Condition Lower progress, so that the photosensitive polymer combination layer of each photosensitive element is sealed at the copper surface of substrate.By so operating, obtain Obtained the stacking that photosensitive polymer combination layer and polyethylene terephthalate film are laminated with the copper surface of substrate Substrate.
(evaluation of sensitivity)
The multilayer board natural cooling that will be obtained, it is being changed into 23 DEG C of time point, in the poly- terephthaldehyde of multilayer board It is closely sealed that there is concentration range 0.00~2.00, concentration period (Concentrated degree ス テ ッ プ) 0.05, exposure meter on sour glycol ester film Size 20mm × 187mm, the size in each stage be 3mm × 12mm 41 sections of stage exposure meters optical tool (photo tool).Hitachi Via Mechanics (strain) systems using wavelength 405nm bluish-violet color laser diode as light source are used directly to retouch machine " DE-1AH " (trade name), so as to pass through optical tool and polyethylene terephthalate with defined energy fluence (light exposure) Film and photosensitive polymer combination layer is exposed.It is explained, the measure use of illumination has been applicable corresponding 405nm probes Ultraviolet illumination photometer (USHIO motors (strain) make, trade name " UIT-150 ") and carry out.
After exposure, polyethylene terephthalate film is peeled off from multilayer board, exposes photosensitive polymer combination layer, 1 mass % aqueous sodium carbonates are sprayed 60 seconds at 30 DEG C, so as to eliminate unexposed portion.By so operating, in base The cured film formed by the solidfied material of photosensitive polymer combination is formd on the copper surface of plate.By being obtained as cured film Stage exposure meter remaining hop count turn into 20 sections when light exposure (mJ/cm2), the sensitivity to photosensitive polymer combination Evaluated.The numerical value is smaller then to represent that sensitivity is better.Show the result in table 3 and 4.
(evaluation of resolution and adaptation)
The use of line width (L)/interval width (S) (being denoted as below " L/S ") is 5/5~30/30 (unit：μm) depiction Case, with the remaining hop count of 41 sections of stage exposure meters as 20 sections energy fluence and to the photoresist group of above-mentioned multilayer board Compound layer is exposed (description).After exposure, the development treatment same with the evaluation of above-mentioned sensitivity has been carried out.
After development, neatly removed in compartment (unexposed portion) and song does not occur for line part (exposed portion) Among the resist pattern formed under the situation of folding (snake) or missing, by the value of minimum line width/interval width to resolution And adaptation is evaluated.The numerical value is smaller then to represent that resolution and adaptation are all better.Show the result in table 3 and 4.
(evaluation of peel property)
For the multilayer board obtained, exposed with the remaining hop count of 41 sections of stage exposure meters as 20 sections of energy fluence Light, polyethylene terephthalate film then is peeled off from multilayer board, exposes photosensitive polymer combination layer, uses 30 DEG C 1 mass % aqueous sodium carbonates and carry out spray development, so as to produce the test film formed with cured film on substrate (40mm×50mm).After the test film is placed into diel at room temperature, entered using 50 DEG C of 3 mass % sodium hydrate aqueous solutions Stripping is gone.The time for being fully exfoliated from substrate removal since the stirring until cured film is set to splitting time.In addition, The size of stripping film after observation is peeled off by visual observation, is evaluated according to following benchmark.Splitting time is shorter, peels off chip size and gets over It is small then to represent that peel property is better.Show the result in table 3 and 4.
(evaluation of plating formative)
For the evaluation by above-mentioned peel property and the test film after the stripping that obtains, seen using light microscope Examine, the minimum plating width that is formed under the situation of broken string or short circuit does not occur according to plating pattern and plating formative is carried out Evaluation.The numerical value is smaller then to represent that plating formative is better.Show the result in table 3 and 4.
(evaluation of plating contaminative)
Each photosensitive element is cut into 40mm × 50mm size, diaphragm is removed and turns into 20 sections with stage exposure meter Light exposure photosensitive polymer combination layer is exposed, peel off polyethylene terephthalate film and solidified Film.After the cured film to be immersed in the plating liquid 3 days of copper sulphate/aqueous sulfuric acid, hull trough test bath ((strain) Yamamoto is used Gold-plated exerciser system) cathode copper plating has been carried out to above-mentioned copper-clad laminated board (substrate).By the plating liquid of no submergence cured film As object of reference, the plating appearance for having used the substrate in the case of the plating liquid for having submerged cured film is observed by visual observation. No contaminative will be judged as in the indistinguishable situation of plating appearance compared with object of reference, there will be the situation of difference to be judged as With contaminative.Show the result in table 3 and 4.
Table 3
Table 4
Comparative example 1 Comparative example 2 Comparative example 3
Sensitivity (mJ/cm2) 35 75 80
Resolution and adaptation (μm) 14 14 14
Peel off residual Nothing Nothing Nothing
Plating formative (μm) 14 14 14
Plating contaminative Nothing Nothing Nothing
Confirm, the direct description exposure of the photosensitive polymer combination of embodiment 1~10 to wavelength 405nm is highly sensitive Degree, resolution, adaptation, peel property and plating formative are excellent, can also prevent plating contaminative.Compare example on the other hand Photoresist of resolution, adaptation and the plating formative of 1~3 photosensitive polymer combination than embodiment 1~10 Composition is poor.In addition, the sensitivity of the photosensitive polymer combination of comparative example 2 and 3 is also insufficient.
According to the present invention, it is possible to provide sensitivity, resolution and excellent adhesion photosensitive polymer combination and make With the manufacture method of its photosensitive element, the forming method of resist pattern and printed circuit board (PCB).

Claims (6)

1. a kind of photosensitive polymer combination, it is to gather containing (A) binder polymer, (B) photopolymerizable compound, (C) light The photosensitive polymer combination of initiator is closed, wherein, (C) Photoepolymerizationinitiater initiater includes the compound shown in following formula (1),
In formula (1), R1And R2The group shown in following formula (1a) or (1b) is represented independently of one another,
In formula (1a) and (1b), R represents the alkyl or phenyl of carbon number 1~20 independently of one another, and multiple R can phase Together also can be different.
2. photosensitive polymer combination according to claim 1, wherein, the very big suction of the compound shown in the formula (1) Wavelength is received as in the range of 350~410nm.
3. photosensitive polymer combination according to claim 1 or 2, wherein, (A) binder polymer contains (first Base) acrylic acid and styrene or styrene derivative be as copolymer composition.
4. a kind of photosensitive element, it possesses supporter, formed on the supporter by any one of claims 1 to 3 institute The photosensitive polymer combination layer that the photosensitive polymer combination stated is formed.
5. a kind of forming method of resist pattern, it includes following process：
Lamination process, the sense formed by photosensitive polymer combination according to any one of claims 1 to 3 is laminated on substrate Photosensitive resin composition layer,
Exposure process, active ray is irradiated to the established part of the photosensitive polymer combination layer,
Developing procedure, the part beyond the established part of the photosensitive polymer combination layer is removed from the substrate, So as to form the resist pattern formed by the solidfied material of the photosensitive polymer combination on the substrate.
6. a kind of manufacture method of printed circuit board (PCB), its include to by the method described in claim 5 and formed with resist pattern The substrate of shape is etched or the process of plating.
CN201710953268.0A 2011-10-20 2012-10-19 Photosensitive polymer combination, photosensitive element, the manufacture method of the forming method of resist pattern and printed circuit board (PCB) Pending CN107652383A (en)

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