CN110095938A - Photosensitive polymer combination - Google Patents
Photosensitive polymer combination Download PDFInfo
- Publication number
- CN110095938A CN110095938A CN201910098289.8A CN201910098289A CN110095938A CN 110095938 A CN110095938 A CN 110095938A CN 201910098289 A CN201910098289 A CN 201910098289A CN 110095938 A CN110095938 A CN 110095938A
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- China
- Prior art keywords
- photosensitive polymer
- polymer combination
- epoxide
- photoepolymerizationinitiater initiater
- mass parts
- Prior art date
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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
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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
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/28—Applying non-metallic protective coatings
- H05K3/285—Permanent coating compositions
- H05K3/287—Photosensitive compositions
Abstract
The purpose of the present invention is to provide a kind of photosensitive polymer combinations, and the undercut of cured coating film is able to suppress forming the cured coating film of thick (such as 40 μm or more thickness) even if on substrate using the composition.Photosensitive polymer combination is characterized in that, photoresist containing (A) containing carboxyl, (B) epoxide, (C) reactive diluent and (D) Photoepolymerizationinitiater initiater, the maximum value of the absorbance of the range of 360nm or more when being measured by ultraviolet-uisible spectrophotometer to (B) epoxide using 0.1 mass % ethyl diethylene glycol (DEG) acetate solution is 0.250 or less, the maximum value of the absorbance of 310nm or more and 360nm range below is 0.020 or more, and 100 mass parts of photoresist relative to (A) containing carboxyl, (B) epoxide described in more than 15 mass parts, also containing (D) Photoepolymerizationinitiater initiater described in more than 0.6 mass parts.
Description
Technical field
The present invention relates to electric with the conductor formed in rigid substrates, flexible base board in lining material, for example for coating
Photosensitive polymer combination used in the insulation-coated material of the conductor circuit pattern of the printing distributing board of road pattern has
The photosensitive polymer combination is coated on film and the dry film of film that is formed and is coated with and makes the photosensitive resin composition
The printing distributing board of solidfied material made of object light solidifies.
Background technique
The conductor circuit pattern that conductor (such as copper foil) is formed on substrate, by welding electro part carrying in the electricity
The insulating coating that circuit part in addition to the solder pad is used as protective film is coated by the solder pad of road pattern.As
Above-mentioned insulating coating is used sometimes comprising the photosensitive of the photoresist containing carboxyl, epoxide and Photoepolymerizationinitiater initiater
The photocuring film of property resin combination.Clarity from insulating coating etc. considers, sometimes requires that above-mentioned insulating coating inhibits
Undercut (undercut).
As being able to suppress the photosensitive polymer combination of undercut, such as propose alkali developable photosensitive resin composition
Object contains the photoresist of (A) containing carboxyl, (B) Photoepolymerizationinitiater initiater, (C) epoxy resin, (D) (methyl) acrylic acid
It is monomer, as (B) Photoepolymerizationinitiater initiater, containing acylphosphine oxide system Photoepolymerizationinitiater initiater, and as (C) epoxy resin,
Contain phenol novolak type epoxy resin, bisphenol A novolac type epoxy resin (patent document 1).
On the other hand, the printing of higher (such as 40 μm or so height) is designed in the height of conductor circuit pattern sometimes
Distributing board is coated insulating coating.In this case, it is necessary to the thickness of insulating coating be made to be coated with to obtain thicker (example on printing distributing board
Thickness such as 40 μm or more).
But if the thickness (such as 40 μm or more thickness) of insulating coating is made to be coated with thicker, active energy ray
(ultraviolet light) is difficult to be transmitted to the lower part of film.If ultraviolet light is difficult to be transmitted to the lower part of film, the light of film lower part is solid
Change becomes inadequate, and undercut occurs in cured coating film.In patent document 1, for by improving the film for being coated with thicker
The photo-curable of lower part inhibit undercut, there is room for improvement tool.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2015-064546 bulletin
Summary of the invention
Subject to be solved by the invention
In view of above-mentioned actual conditions, though the purpose of the present invention is to provide formed on substrate it is thicker (such as 40 μm with
On thickness) cured coating film be also able to suppress cured coating film undercut photosensitive polymer combination, have the photonasty
Resin combination is coated on film and the printing of the dry film of the film that is formed, photocuring film with the photosensitive polymer combination is matched
Line plate.
Means for solving the problems
The solution of the present invention is a kind of photosensitive polymer combination, which is characterized in that contains the photonasty of (A) containing carboxyl
Resin, (B) epoxide, (C) reactive diluent and (D) Photoepolymerizationinitiater initiater use 0.1 mass % ethyl diethylene glycol (DEG) second
Acid esters solution, when being measured by ultraviolet-uisible spectrophotometer to (B) epoxide, the range of 360nm or more
The maximum value of absorbance be 0.250 hereinafter, the maximum value of the absorbance of 310nm or more and 360nm range below is 0.020
More than, 100 mass parts of photoresist relative to (A) containing carboxyl, (B) epoxy described in more than 15 mass parts
Compound, and contain (D) Photoepolymerizationinitiater initiater described in more than 0.6 mass parts.
The solution of the present invention is a kind of photosensitive polymer combination, which is characterized in that (B) epoxide includes to make
With 0.1 mass % ethyl diethylene glycol (DEG) acetate solution by ultraviolet-uisible spectrophotometer measure when 320nm or more and 360nm with
Under range absorbance maximum value be 0.020 or more epoxide.
The solution of the present invention is a kind of photosensitive polymer combination, which is characterized in that (B) epoxide includes to make
With 0.1 mass % ethyl diethylene glycol (DEG) acetate solution by ultraviolet-uisible spectrophotometer measure when 340nm or more and 360nm with
Under range absorbance maximum value be 1.0 or more epoxide.
The solution of the present invention is a kind of photosensitive polymer combination, which is characterized in that (B) epoxide includes choosing
From 2 function naphthalene type epoxy resins, biphenyl type epoxy resin, xenol aralkyl-type epoxy resin and dimer acid glycidyl ester type
At least one of epoxy resin.
The solution of the present invention is a kind of photosensitive polymer combination, which is characterized in that (D) Photoepolymerizationinitiater initiater contains
Alpha-aminoalkyl phenyl ketone (α-amino alkyl phenone) class Photoepolymerizationinitiater initiater.
The solution of the present invention is a kind of photosensitive polymer combination, which is characterized in that (D) Photoepolymerizationinitiater initiater contains
Alpha-aminoalkyl phenyl ketone Photoepolymerizationinitiater initiater and oxime esters Photoepolymerizationinitiater initiater.
The solution of the present invention is a kind of dry film, which is characterized in that has the photosensitive polymer combination being coated on film
Made of film.
The solution of the present invention is a kind of printing distributing board, which is characterized in that the light with the photosensitive polymer combination
Cured film.
The effect of invention
According to the solution of the present invention, the 0.1 mass % ethyl diethylene glycol (DEG) acetate solution of (B) epoxide is used to pass through
Ultraviolet-uisible spectrophotometer measurement 360nm or more range absorbance maximum value be 0.25 hereinafter, 310nm or more and
The maximum value of the absorbance of 360nm range below is 0.02 or more, and the photoresist relative to (A) containing carboxyl
100 mass parts also cause containing (D) photopolymerization more than 0.6 mass parts containing (B) epoxides more than 15 mass parts
Agent, to also be able to suppress cured coating film even if forming the cured coating film of thick (such as 40 μm or more thickness) on substrate
Undercut.
According to the solution of the present invention, by the inclusion of use 0.1 mass % ethyl diethylene glycol (DEG) acetate solution by it is ultraviolet can
See the absorbance of the 320nm or more when spectrophotometer is measured (B) epoxide and 360nm range below most
The epoxide that big value is 0.02 or more, to can also further suppress cured coating film even if forming thick cured coating film
Undercut.
According to the solution of the present invention, by the inclusion of use 0.1 mass % ethyl diethylene glycol (DEG) acetate solution by it is ultraviolet can
See the absorbance of the 340nm or more when spectrophotometer is measured (B) epoxide and 360nm range below most
The epoxide that big value is 1.0 or more, to also can more reliably inhibit cured coating film even if forming thick cured coating film
Undercut, superior wire shaped can be obtained.
According to the solution of the present invention, contain alpha-aminoalkyl phenyl ketone photopolymerization by (D) Photoepolymerizationinitiater initiater to cause
Agent and oxime esters Photoepolymerizationinitiater initiater, to also can more reliably inhibit cured coating film even if forming thick cured coating film
Undercut.
Specific embodiment
Next, being carried out to photosensitive polymer combination of the invention as described below.Photosensitive resin composition of the invention
Object contains the photoresist of (A) containing carboxyl, (B) epoxide, (C) reactive diluent and (D) Photoepolymerizationinitiater initiater,
The 0.1 mass % ethyl diethylene glycol (DEG) acetate solution of use of above-mentioned (B) epoxide is surveyed by ultraviolet-uisible spectrophotometer
The maximum value of the absorbance of the range of fixed 360nm or more is for 0.250 hereinafter, the suction of 310nm or more and 360nm range below
The maximum value of luminosity is 0.020 or more, and 100 mass parts of photoresist relative to above-mentioned (A) containing carboxyl, contains 15
Above-mentioned (B) epoxide more than mass parts, also containing above-mentioned (D) Photoepolymerizationinitiater initiaters more than 0.6 mass parts.
(A) containing the photoresist of carboxyl
Photoresist containing carboxyl is not particularly limited, such as can be enumerated unsaturated double with 1 or more photonasty
The resin of key.As the photoresist containing carboxyl, such as the modified by polyacid epoxy (first obtained as follows can be enumerated
Base) the free-radical polymerised unsaturated monocarboxylic epoxy resin of modified by polyacid such as acrylate etc.: make acrylic acid, metering system
Sour (hereinafter sometimes referred to " (methyl) acrylic acid ".) etc. free-radical polymerised unsaturated monocarboxylic in 1 molecule have 2 with
On epoxy group polyfunctional epoxy resin epoxy group at least part reaction, obtain epoxy (methyl) acrylate etc. from
By base polymerism unsaturated monocarboxylic epoxy resin, and then make the free-radical polymerised insatiable hunger of polyacid or its acid anhydrides and generation
Hydroxyl reaction with mono-carboxylic acid's epoxy resin obtains.
As long as above-mentioned multi-functional epoxy resin is the epoxy resin of 2 functions or more, special limit is had no to chemical structure
It is fixed, it can use.In addition, being not particularly limited to the epoxide equivalent of multi-functional epoxy resin, for example, its upper limit value is preferred
3000g/eq, more preferable 2000g/eq, further preferred 1000g/eq, particularly preferred 500g/eq.On the other hand, lower limit value
It is preferred that 100g/eq, particularly preferred 200g/eq.
As multi-functional epoxy resin, such as biphenyl aralkyl-type epoxy resin, phenyl aralkyl-type can be enumerated
Epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, modifying epoxy resin by organosilicon
The phenol novolac of equal rubber modified epoxy resins, 6-caprolactone modified epoxy, bisphenol A-type, bisphenol-f type, bisphenol-A D type etc.
The cresol novolak type epoxy resins such as type epoxy resin, o-cresol phenolic varnish type, bisphenol A novolac type ring oxygen
Resin, annular aliphatic polyfunctional epoxy resin, glycidyl ester type polyfunctional epoxy resin, glycidic amine type polyfunctional ring
Oxygen resin, hetero ring type polyfunctional epoxy resin, bis-phenol modified novolac type epoxy resin, multifunctional modified novolac type ring
Oxygen resin etc..In addition, the product for being further introduced into the halogen atoms such as Br, Cl in these resins can also be used.These more officials
Energy property epoxy resin can be used alone, and also two or more may be used.
Free-radical polymerised unsaturated monocarboxylic is not particularly limited, for example, can enumerate (methyl) acrylic acid, bar
Beans acid, cinnamic acid etc..Wherein, from the aspect of being easy to get and handling, preferred (methyl) acrylic acid.These free radical polymerizations
Property unsaturated monocarboxylic can be used alone, and also two or more may be used.
The reaction method of multi-functional epoxy resin and free-radical polymerised unsaturated monocarboxylic is not particularly limited, example
It such as can be and multi-functional epoxy resin and free-radical polymerised unsaturated monocarboxylic be heated in diluent appropriate
Make its reaction.
Polyacid or multi-anhydride with pass through the anti-of multi-functional epoxy resin and free-radical polymerised unsaturated monocarboxylic
The hydroxyl reaction answered and generated, so that free carboxyl is introduced photoresist.By the way that the carboxyl to dissociate is introduced photonasty
Resin, to assign alkali-developable to photoresist.Polyacid or its acid anhydrides are not particularly limited, is saturated, is unsaturated
Polyacid or its acid anhydrides all can be used.In polyacid, such as succinic acid, maleic acid, adipic acid, citric acid, neighbour can be enumerated
Phthalic acid, tetrahydrophthalic acid, 3- methyl tetrahydrophthalic acid, 4- methyl tetrahydrophthalic acid, 3- ethyl tetrahydro
Phthalic acid, 4- ethyl tetrahydrophthalic acid, hexahydrophthalic acid, 3- methylhexahydrophthaacid acid, 4- methyl six
Hydrogen phthalic acid, 3- ethyl hexahydrophthalic acid, 4- ethyl hexahydrophthalic acid, methyl tetrahydrophthalic acid, first
Base hexahydrophthalic acid, endo-methylene group tetrahydrophthalic acid, methylendomethylene tetrahydrophthalic acid, trimellitic acid,
Pyromellitic Acid and diglycolic acid etc. can enumerate the acid anhydrides of above-mentioned polyacid as multi-anhydride.These compounds can be independent
Ground uses, and also two or more may be used.
In the present invention, the free-radical polymerised unsaturated monocarboxylic epoxy resin of above-mentioned modified by polyacid be can be used as
Photoresist containing carboxyl uses, as needed, can by make to have 1 or more free-radical polymerised unsaturated group with
The glycidyl compound of epoxy group and the free-radical polymerised unsaturated monocarboxylic epoxy resin of above-mentioned modified by polyacid
Carboxyl reaction, to be further introduced into free-radical polymerised unsaturated group, be made further increase photonasty contain carboxylic
The photoresist of base.The photoresist containing carboxyl for further increasing photonasty is due to passing through above-mentioned glycidyl
The reaction of compound and by free-radical polymerised unsaturated group introduce the free-radical polymerised unsaturated monocarboxylic of modified by polyacid
Change the side chain of epoxy backbone, therefore, photopolymerization reaction is high, can play superior photobehavior.As with 1
The compound of above free-radical polymerised unsaturated group and epoxy group, such as glycidyl acrylate, methyl can be enumerated
Glycidyl acrylate, allyl glycidyl ether, pentaerythritol triacrylate monoglycidyl ether, pentaerythrite three
Methacrylate monoglycidyl ether etc..It should be noted that glycidyl can have in 1 molecule it is multiple.Above-mentioned tool
Having the compound of 1 or more free-radical polymerised unsaturated group and epoxy group can be used alone, can also be by two or more simultaneously
With.
The acid value of photoresist containing carboxyl is not particularly limited, for example, from alkali-developable is reliably obtained
From the aspect of, lower limit value preferred 30mgKOH/g, particularly preferred 40mgKOH/g.On the other hand, for example, from alkaline developer is prevented
Cause exposure portion dissolve from the aspect of, the preferred 200mgKOH/g of the upper limit value of acid value, from prevent photocured product moisture-proof and
From the aspect of the deterioration of electrical characteristics, particularly preferred 150mgKOH/g.
In addition, being not particularly limited to the matter average molecular weight of the photoresist containing carboxyl, for example, from photocured product
From the aspect of obdurability and dry to touch, lower limit value preferably 6000, more preferable 7000, particularly preferred 8000.Another party
Face, for example, from the aspect of smoothly alkali-developable, the upper limit value of matter average molecular weight preferably 200000, more preferable 100000,
Particularly preferred 50000.
Above-mentioned each raw material can be used to synthesize by above-mentioned reaction process for photoresist containing carboxyl, it is possible to use city
The photoresist containing carboxyl sold.As the commercially available photoresist containing carboxyl, such as " SP- can be enumerated
4621 " (Showa Denko K. K), " ZAR-2000 ", " ZFR-1122 ", " FLX-2089 ", " ZCR-1569H " (the above are days
The manufacture of this chemical drug Co., Ltd.), " CYCLOMERP (ACA) Z-250 " (Daicel-Allnex Ltd.) etc..In addition, these contain
The photoresist of carboxyl can be used alone, and also two or more may be used.
(B) epoxide
For epoxide joined together in the present invention, pass through purple using 0.1 mass % ethyl diethylene glycol (DEG) acetate solution
The maximum value of the absorbance of the range of the 360nm or more of outer visible spectrophotometer measurement is 0.250 hereinafter, and using 0.1
The 310nm or more and 360nm that quality % ethyl diethylene glycol (DEG) acetate solution is measured by ultraviolet-uisible spectrophotometer are below
The maximum value of the absorbance of range is 0.020 or more.In addition, relative to the 100 mass parts (solid of photoresist containing carboxyl
Ingredient, it is same as below.), cooperate the epoxide with above-mentioned absorbance of 15 mass parts or more.By relative to containing carboxylic
100 mass parts of photoresist of base cooperate the epoxide with above-mentioned absorbance of 15 mass parts or more, purple in irradiation
Outside line (such as range of 310~400nm of wavelength) and the photocuring film that thick (such as 40 μm or more thickness) is formed on substrate
When, the photonasty of photosensitive polymer combination improves, and helps to inhibit undercut.
As long as being measured using 0.1 mass % ethyl diethylene glycol (DEG) acetate solution by ultraviolet-uisible spectrophotometer
The maximum value of the absorbance of 310nm or more and 360nm range below is 0.020 or more, then is not particularly limited, from further
The photonasty for ultraviolet light is improved, thus from the aspect of further suppressing undercut, more preferable 0.050 or more, particularly preferably
0.100 or more.
In addition, for using 0.1 mass % ethyl diethylene glycol (DEG) acetate solution to measure by ultraviolet-uisible spectrophotometer
320nm or more and the maximum value of the absorbance of 360nm range below for, as long as above-mentioned 310nm or more and 360nm or less
Absorbance maximum value be 0.020 or more, then be not particularly limited, from the aspect of further suppressing undercut, preferably
0.020 or more, more preferable 0.050 or more, particularly preferred 0.070 or more.In addition, about 0.1 matter for using epoxide
The 340nm or more and 360nm model below that amount % ethyl diethylene glycol (DEG) acetate solution is measured by ultraviolet-uisible spectrophotometer
The maximum value for the absorbance enclosed, as long as the maximum value of above-mentioned 310nm or more and 360nm absorbance below is 0.020 or more,
It is not particularly limited, from the aspect of further suppressing undercut, preferably 0.020 or more, more preferable 0.050 or more, it is especially excellent
Select 1.000 or more.
On the other hand, it is measured using 0.1 mass % ethyl diethylene glycol (DEG) acetate solution by ultraviolet-uisible spectrophotometer
360nm or more range absorbance maximum value as long as be 0.250 hereinafter, as long as be not particularly limited, from further increasing
Photosensitive polymer combination for ultraviolet light it is photosensitive from the aspect of, more preferable 0.150 hereinafter, particularly preferred 0.100 with
Under.
In the 360nm measured using 0.1 mass % ethyl diethylene glycol (DEG) acetate solution by ultraviolet-uisible spectrophotometer
The maximum value of the absorbance of above range is 0.250 or less and is led to using 0.1 mass % ethyl diethylene glycol (DEG) acetate solution
Cross ultraviolet-uisible spectrophotometer measurement 310nm or more and the absorbance of 360nm range below maximum value be 0.020 with
On epoxide in, preferably by 310nm or more of more than two kinds and the maximum of the above-mentioned absorbance of 360nm range below
The epoxide that value is 0.020 or more is used in combination, that is, most by the above-mentioned absorbance of 310nm or more and 360nm range below
The big different epoxide of value (0.020 or more) is used in combination.Wherein, from the aspect of further suppressing undercut, relative to
The maximum value of the above-mentioned absorbance of 320nm or more and 360nm range below is 0.030 100 mass of epoxide below
Part, the maximum value for preferably comprising the above-mentioned absorbance of 320nm or more and the 360nm range below of 50~300 mass parts is more than
0.030 epoxide, further preferably 100~250 mass parts particularly preferably contain 120~200 mass parts.In addition, from
From the aspect of further suppressing undercut, wherein preferably with respect to 340nm or more and the above-mentioned extinction of 360nm range below
The maximum value of degree be 0.010 100 mass parts of epoxide below, preferably comprise the 340nm or more of 50~300 mass parts and
The maximum value of the above-mentioned absorbance of 360nm range below is more than 1.000 epoxide, further preferably 100~250 matter
Part is measured, 120~200 mass parts are particularly preferably contained.The maximum value of the above-mentioned absorbance of range as 360nm or more is
The epoxy that the maximum value of the above-mentioned absorbance of 0.250 or less and 310nm or more and 360nm range below is 0.020 or more
Compound, for example, can enumerate 2 function naphthalene type epoxy resins, biphenyl type epoxy resin, xenol aralkyl-type epoxy resin,
Dimer acid glycidyl ester type epoxy resin, naphthols cresol novolak type epoxy resin, imide-type epoxy resin etc..These
Compound can be used alone, and also two or more may be used.
In addition, the use level about the epoxide with above-mentioned absorbance, as long as relative to the photosensitive of carboxyl is contained
Property 100 mass parts of resin, be 15 mass parts or more, be then not particularly limited, for example, for its lower limit value, from more reliably
From the aspect of the undercut for inhibiting photocuring film, relative to 100 mass parts of photoresist containing carboxyl, preferably 18 mass
Part, more preferable 20 mass parts, particularly preferred 22 mass parts.On the other hand, for the epoxide with above-mentioned absorbance
The upper limit value of use level, from the aspect of developability, relative to 100 mass parts of photoresist containing carboxyl, preferably 100
Mass parts, more preferable 50 mass parts, particularly preferred 30 mass parts.
(C) reactive diluent
Reactive diluent is, for example, photopolymerization monomer, is that every 1 molecule has at least one, preferably 2 or more polymerisms double
The compound of key.In order to which the photocuring to photosensitive polymer combination carries out reinforcement, obtains having sufficient acid resistance, heat-resisting
Property, alkali resistance etc. solidfied material and use reactive diluent.
As reactive diluent, such as (methyl) acrylate compounds of simple function can be enumerated, more than 2 functions
(methyl) acrylate compounds.As (methyl) acrylate compounds, such as (methyl) acrylic acid 2- hydroxyl can be enumerated
Base ethyl ester, (methyl) phenoxyethyl acrylate, diglycol monotertiary (methyl) acrylate, (methyl) acrylic acid 2- hydroxyl -3- benzene
The simple functions such as oxygroup propyl ester (methyl) acrylate compounds, 1,4-butanediol two (methyl) acrylate, 1,6- hexylene glycol two
(methyl) acrylate, neopentyl glycol two (methyl) acrylate, diethylene glycol (deg) two (methyl) acrylate, neopentyl glycol adipic acid
Ester two (methyl) acrylate, hydroxy new pentane acid neopentyl glycol two (methyl) acrylate, Bicvclopentyl two (methyl) acrylic acid
Ester, ethylene-oxide-modified di(2-ethylhexyl)phosphate (methyl) acrylate, allylation cyclohexyl two (methyl) acrylate, isocyanuric acid ester
Two (methyl) acrylate etc. 2 functions (methyl) acrylate compounds, trimethylolpropane tris (methyl) acrylate, two
(trimethylolpropane) four (methyl) acrylate, dipentaerythritol three (methyl) acrylate, pentaerythrite three (methyl) third
Olefin(e) acid ester, epoxy pronane modification trimethylolpropane tris (methyl) acrylate, isocyanuric acid three (acryloyl-oxyethyl) ester,
Propionic acid is modified the (first of 3 functions such as dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate or more
Base) more than acrylate compounds and simple function or 2 functions carbamate (methyl) esters of acrylic acid etc..These are anti-
Answering property diluent can be used alone, and can also be used in mixed way two or more.Special limit is had no to the content of reactive diluent
It is fixed, relative to 100 mass parts of photoresist containing carboxyl, preferably 5.0 mass parts~100 mass parts, particularly preferred 10 matter
Measure part~50 mass parts.
(D) Photoepolymerizationinitiater initiater
In the present invention, relative to 100 mass parts of photoresist containing carboxyl, cooperate the photopolymerization of 0.6 mass parts or more
Initiator.Relative to 100 mass parts of photoresist containing carboxyl, caused by photopolymerization more than 0.6 mass parts of cooperation
Agent is formed thick (such as 40 μm or more thickness) on substrate in irradiation ultraviolet light (such as range of 310~400nm of wavelength)
Photocuring film when, the photonasty of photosensitive polymer combination improves, and helps to inhibit undercut.
For the use level of Photoepolymerizationinitiater initiater, relative to 100 mass parts of photoresist containing carboxyl, as long as being
It more than 0.6 mass parts, is then not particularly limited, for example, for its lower limit value, from the aspect of further suppressing undercut,
Relative to 100 mass parts of photoresist containing carboxyl, preferably 0.7 mass parts, particularly preferred 1.0 mass parts.On the other hand,
For the upper limit value of the use level of Photoepolymerizationinitiater initiater, for example, increasing from the line width for being reliably prevented cured coating film and making ruler
From the aspect of very little precision reduces, relative to 100 mass parts of photoresist containing carboxyl, preferably 10 mass parts are especially excellent
Select 6.0 mass parts.
The chemical structure of Photoepolymerizationinitiater initiater is not particularly limited, can be used, but preferably comprise alpha-aminoalkyl benzene
Base ketone Photoepolymerizationinitiater initiater and/or oxime esters Photoepolymerizationinitiater initiater.As Photoepolymerizationinitiater initiater, by cooperating alpha-aminoalkyl
Phenyl ketone Photoepolymerizationinitiater initiater and/or oxime esters Photoepolymerizationinitiater initiater, photosensitive polymer combination of the invention is for ultraviolet
The photonasty of line further increases, and helps more reliably to inhibit undercut.Think this and alpha-aminoalkyl phenyl ketone photopolymerization
It is related that initiator and oxime esters Photoepolymerizationinitiater initiater mainly play its function under the wavelength of 380nm or more.Wherein, more preferably extremely
Contain alpha-aminoalkyl phenyl ketone Photoepolymerizationinitiater initiater less, particularly preferably causes containing the ketone photopolymerization of alpha-aminoalkyl phenyl
Agent and oxime esters Photoepolymerizationinitiater initiater.
As alpha-aminoalkyl phenyl ketone Photoepolymerizationinitiater initiater, such as 2- benzyl -2- dimethylamino-can be enumerated
1- (4- morphlinophenyl)-butanone-1,2- methyl-1-[4- (methyl mercapto) phenyl]-2- morpholino propane-1- ketone etc..These are changed
Closing object can be used alone, and also two or more may be used.
In addition, oxime esters Photoepolymerizationinitiater initiater is the Photoepolymerizationinitiater initiater with oxime ester base.Draw as oxime esters photopolymerization
Agent is sent out, such as 1,2- acetyl caproyl, 1- [4- (thiophenyl) -2- (O- benzoyl oximes)], ethyl ketone 1- [9- ethyl-can be enumerated
6- (2- methyl benzoyl) -9H- carbazole -3- base] -1- (0- acetyl group oxime), 2- (Acetyloxyimino methyl) thioxanthene -9-
Ketone, 1,8- acetyl caproyl, 1,8- bis- [9- ethyl -6- nitro -9H- carbazole -3- bases] -, 1,8- bis- (O- acetyl group oximes), 1,8- pungent two
Ketone, 1,8- bis- [9- (2- ethylhexyl) -6- nitro -9H- carbazole -3- bases] -, 1,8- bis- (O- acetyl group oximes), (Z)-(9- second
Base -6- nitro -9H- carbazole -3- base) (4- ((1- methoxy propane -2- base) oxygen) -2- aminomethyl phenyl) ketone O- acetyl group oxime
Deng.These compounds can be used alone, and also two or more may be used.
In the case where containing alpha-aminoalkyl phenyl ketone Photoepolymerizationinitiater initiater and oxime esters Photoepolymerizationinitiater initiater, to α-
Aminoalkyl-phenones class Photoepolymerizationinitiater initiater/oxime esters Photoepolymerizationinitiater initiater mass ratio is not particularly limited, preferably 1.0~
10 range, more preferable 1.5~5.0 range, particularly preferred 2.0~4.0 range.
In addition, in the present invention, as Photoepolymerizationinitiater initiater, alpha-aminoalkyl phenyl ketone Photoepolymerizationinitiater initiater can be cooperated
With the Photoepolymerizationinitiater initiater (other Photoepolymerizationinitiater initiaters) other than oxime esters Photoepolymerizationinitiater initiater.In addition, in addition to alpha-aminoalkyl
Other than phenyl ketone Photoepolymerizationinitiater initiater and/or oxime esters Photoepolymerizationinitiater initiater, other photopolymerization can also be further cooperated to draw
Send out agent.As other Photoepolymerizationinitiater initiaters, such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzene idol can be enumerated
Relation by marriage isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylamino benzoylformaldoxime, 2,2- dimethoxy
Base -2- phenyl acetophenone, 2,2- diethoxy -2- phenyl acetophenone, 2- hydroxy-2-methyl -1- phenyl-propane -1- ketone, 1- hydroxyl
Butylcyclohexyl phenyl ketone, 4- (2- hydroxyl-oxethyl) phenyl -2- (hydroxyl -2- propyl) ketone, benzophenone, p- phenyl hexichol first
Ketone, 4,4 '-diethylamino benzophenone, dichloro benzophenone, 2-methylanthraquinone, 2- ethyl hydrazine, 2- tert-butyl anthraquinone, 2-
Amino anthraquinones, 2- methyl thioxanthones, 2- ethyl thioxanthones, 2-chlorothioxanthone, 2,4- dimethyl thioxanthone, 2,4- diethyl thioxanthene
Ketone, benzil dimethyl ketal, acetophenone dimethyl ketal, p- dimethyl amino benzoate, 2,4,6- trimethylbenzene first
Acyl group diphenyl phosphine oxide, bis- (2,4,6- trimethylbenzoyl) phenyl phosphine oxides, bis- (2,6- Dimethoxybenzoyls)-
2,4,4- trimethyl-pentyl phosphine oxide, (2,4,6- trimethylbenzoyl) ethoxyl phenenyl phosphine oxide etc..These compounds can
It is used alone, also two or more may be used.
In the present invention, other than above-mentioned (A) ingredient~(D) ingredient, other compositions, example can suitably be cooperated as needed
Such as extender pigment, colorant, various additives, fire retardant, non-reactive diluent.
As extender pigment, such as talcum, barium sulfate, hydrophobic silica, aluminium oxide, hydroxide can be enumerated
Aluminium, mica etc..Colorant is pigment, pigment etc., is not particularly limited, in addition, white color agents, blue colorant, green
Toner, yellow colorants, violet colorant, black colorant etc. can be used.In above-mentioned colorant, such as it can enumerate
Inorganic system's colorant such as the titanium oxide as white color agents, the carbon black as black colorant.Furthermore it is possible to enumerate conduct
Phthalocyanines systems such as the phthalocyanine green of green colourant, the phthalocyanine blue as blue colorant, thunder Austria Nore blue (Lionolblue) etc. have
Machine system colorant.
In various additives, the defoaming agent, dicyandiamide of organic silicon-type, hydrocarbon system and acrylic acid series etc. can be enumerated
(DICY) and its derivative, melamine and its derivative, boron trifluoride-amine complex, organic acid hydrazides, diamino malononitrile
(DAMN) and its curing accelerators such as derivative, guanamines and its derivative, amine acid imide (amine imide, AI) and polyamines,
Thixotropic agent etc..
As fire retardant, such as phosphorus flame retardant can be enumerated.As phosphorus flame retardant, such as tricresyl phosphate can be enumerated
(chloroethyl) ester, tricresyl phosphate (bis- chloropropyl of 2,3-) ester, tricresyl phosphate (2- chloropropyl) ester, tricresyl phosphate (2,3- bromopropyl) ester, phosphorus
Sour three (bromine chloropropyl) esters, phosphoric acid 2,3- dibromopropyl -2,3- chlorine propyl ester, tricresyl phosphate (tribromo phenyl) ester, tricresyl phosphate (dibromobenzene
Base) phosphate containing halogen system such as ester, tricresyl phosphate (tribromo neopentyl) ester；Trimethyl phosphate, triethyl phosphate, tributyl phosphate,
The non-halogens aliphatic phosphate ester such as trioctyl phosphate, tributoxyethyl phosphate；Triphenyl phosphate, tricresyl phosphate base diphenyl
Ester, di(2-ethylhexyl)phosphate (tolyl) phenylester, tricresyl phosphate (toluene) ester, tricresyl phosphate (dimethylbenzene) ester, di(2-ethylhexyl)phosphate cresyl diphenyl phosphate,
Tricresyl phosphate (isopropyl phenyl) ester, p isopropylbenzoic acid base phenyl diphenyl, phosphoric acid diisopropyl phenyl phenylester, tricresyl phosphate (three
Aminomethyl phenyl) the non-halogen such as ester, tricresyl phosphate (tert-butyl phenyl) ester, phosphoric acid hydroxy phenyl diphenyl, octyl diphenyl phosphate
Prime system aromatic phosphoric ester；Three (diethyl hypophosphorous acid) aluminium, three (Methylethyl hypophosphorous acid) aluminium, three (diphenyl hypophosphorous acid) aluminium,
Bis- (diethyl hypophosphorous acid) zinc, bis- (Methylethyl hypophosphorous acid) zinc, bis- (diphenyl hypophosphorous acid) zinc, bis- (diethyl hypophosphorous acid) oxygen
Titanium, four (diethyl hypophosphorous acid) titaniums, bis- (Methylethyl hypophosphorous acid) oxygen titaniums, four (Methylethyl hypophosphorous acid) titaniums, bis- (diphenyl
Phosphoric acid) hypophosphorous acid metal salts, diphenylacetylene phosphine oxide, the triphenylphosphine oxide, three such as oxygen titanium, four (diphenyl hypophosphorous acid) titaniums
Phosphine oxides based compounds such as alkyl phosphine oxide, three (hydroxy alkyl) phosphine oxides etc..These can be used alone, can also be by 2 kinds
It is used in combination above.In these, the preferred fire retardant of organic phosphate system.
Non-reactive diluent is for adjusting viscosity, drying property, coating of photosensitive polymer combination etc..As non-anti-
Answering property diluent, such as organic solvent can be enumerated.In organic solvent, such as methyl ethyl ketone, cyclohexanone can be enumerated etc.
Ketone；Toluene, dimethylbenzene etc. are aromatic hydrocarbon；The alcohols such as methanol, isopropanol, cyclohexanol；The alicyclic rings such as hexamethylene, hexahydrotoluene
Formula hydro carbons；The dioxanes such as cellosolve, butyl cellosolve；The carbitols class such as carbitol, butyl carbitol；Ethyl acetate, acetic acid
Butyl ester, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, acetate of butyl carbitol, diethylene glycol monomethyl ether
Esters such as acetic acid esters, ethyl diethylene glycol (DEG) acetic acid esters etc..These solvents can be used alone, and also two or more may be used.
The manufacturing method of the photosensitive polymer combination of aforementioned present invention is not limited to specific method, such as can be
With regulated proportion by after above-mentioned each components matching, the kneading devices such as three rollers, ball mill, sand mill or super are used at room temperature
The agitating devices such as grade mixing machine, planetary-type mixer are kneaded or are mixed and manufactured.In addition, in above-mentioned mixing or mixing it
Before, it can be kneaded or be pre-mixed in advance as needed.
Next, being illustrated for user's rule of the photosensitive polymer combination of aforementioned present invention.Here, first
First, illustrating has the high circuit pattern of height (such as the circuit of 40 μm or so of height for etching copper foil and being formed
Pattern) printing distributing board on be coated with photosensitive polymer combination of the invention and the method that forms solder mask.
It is recessed using silk-screen printing, flush coater, bar coater, spreader, scraper plate coating machine, knife type coater, roll coater, photograph
Method well known to version coating machine etc., by above-mentioned photosensitive polymer combination with desired thickness (such as 40 μm or more thickness)
It is coated on the printing distributing board with the circuit pattern for forming copper foil etching.It is as needed, photosensitive in order to make after coating
Property resin combination in non-reactive diluent (organic solvent) volatilization, carry out 60~80 DEG C or so at a temperature of heat 15
Predrying in~60 minutes or so, makes non-reactive diluent volatilize from photosensitive polymer combination, make the surface of film at
For inviscid state.Make to have on the photosensitive polymer combination of coating and becomes saturating other than the pad for making foregoing circuit pattern
The minus film of the pattern of photosensitiveness is closely sealed, irradiates ultraviolet light (for example, range of 310~400nm of wavelength) from thereon.Then, pass through
Non-exposed areas corresponding with above-mentioned pad is removed with dilute alkaline aqueous solution, so that film be made to develop.For developing method, use
Spray-on process, spray process etc., as used dilute alkaline aqueous solution, such as can enumerate 0.5~5 mass % sodium carbonate it is water-soluble
Liquid.Next, by solidifying after carrying out 20~80 minutes at 130~170 DEG C with drying machine of heated air circulation type etc., so as to
Cured coating film, that is, solder mask of target is formed on printing distributing board.It should be noted that can replace irradiating ultraviolet light from minus film
Without the use of minus film, ultraviolet light is irradiated using exposure device is directly retouched.
Next, explanation is in the circuit pattern for having the height for etching copper foil and being formed high (for example, 40 μm or so of height
The circuit pattern of degree) printing distributing board on, using being coated with dry film made of photosensitive polymer combination of the invention, formed
The method of solder mask.
Dry film becomes stepped construction, and the stepped construction includes support membrane (for example, polyethylene terephthalate
The thermoplastic films such as film, polyester film), be coated on the solder mask of support membrane and for protecting the cover film of solder mask (for example, polyethylene
Film, polypropylene screen).Photosensitive polymer combination is applied on support membrane using method well known to rolling method etc. desired
After thickness (such as 40 μm or more thickness), film is dried, forms solder mask on support membrane.Then, pass through
The laminated cover film on solder mask, so as to make dry film.By will resistance while by the covering film stripping of above-mentioned dry film
Layer and printing distributing board fitting, to form solder mask on printing distributing board.Then, it is exposed by being measured in the same manner as described above
Light, development, rear cured each process, so as to form the solder mask with the circuit pattern of target on printing distributing board.
Embodiment
Next, being illustrated to the embodiment of the present invention, as long as the present invention is not limited to this not past its purport
A little embodiments.
Examples 1 to 8, comparative example 1~3
With mixing ratio shown in following table 1 by each components matching shown in following table 1, made at room temperature using three rollers
It mixes dispersion, photosensitive polymer combination used in preparation Examples 1 to 8, comparative example 1~3.Shown in following table 1
The use level of each ingredient is as long as no special instructions, then it represents that mass parts.It should be noted that the empty column portion of the use level in following table 1
Expression is mismatched.In addition, described in following table 2 using 0.1 mass % ethyl diethylene glycol (DEG) acetate solution by it is ultraviolet can
See the absorbance of provision wavelengths when spectrophotometer is measured epoxide.Ultraviolet-uisible spectrophotometer uses day
The U-3310 type spectrophotometer of vertical production Co., Ltd., institute.The setup parameter of spectrophotometer is set as measurement wave-length coverage
200nm~400nm, sampling interval 0.50nm, slit 2nm, the long 10mm in pond.
[table 1]
[table 2]
* the absorbance of epoxide is to pass through purple using 0.1 mass % ethyl diethylene glycol (DEG) acetate solution of epoxide
The absorbance of outer visible spectrophotometer measurement.
It should be noted that the details about each ingredient in table 1 is as described below.
(A) containing the photoresist of carboxyl
KAYARAD ZAR-2000: solid component (resin point) 65 mass %, Nippon Kayaku K. K
It should be noted that KAYARAD ZAR-2000 is the modified by polyacid epoxy acrylic ester structure obtained as follows, i.e., make propylene
Acid is reacted at least part of the epoxy group of epoxy resin (bisphenol A type epoxy resin), obtains epoxy acrylate, and make more
First acid is reacted with the hydroxyl generated to be obtained.
(B) epoxide
HP-4032:DIC Co., Ltd.
NC-3000: Nippon Kayaku K. K
JER871: Mitsubishi chemical Co., Ltd
YX-4000K: Mitsubishi chemical Co., Ltd
(C) reactive diluent
EBERCRYL8405:Daicel-Allnex Ltd.
(D) Photoepolymerizationinitiater initiater
NCI-831: oxime esters Photoepolymerizationinitiater initiater, ADEKA Corp.
OXE-02: oxime esters Photoepolymerizationinitiater initiater, BASF AG
Irgacure 369: alpha-aminoalkyl phenyl ketone Photoepolymerizationinitiater initiater, BASF AG
Extender pigment
HIGILITE H42M: Showa Denko K. K
Fire retardant
Exolit OP-935: Clariant Amada Co., Ltd.
Curing accelerator
MELAMINE: Nissan Chemical Ind Ltd
DICY-7: Mitsubishi chemical Co., Ltd
Defoaming agent
X-50-1095C: Shin-Etsu Chemial Co., Ltd
Colorant
DENKA BLACK: Deuki Kagaku Kogyo Co., Ltd
Non-reactive diluent
EDGAC: Sanyo is melted into product Co., Ltd.
(B) epoxide other than ingredient
EPICRON 850-S:DIC Co., Ltd.
EXA-4710:DIC Co., Ltd.
Test film production process
Substrate: polyimide film is (12 μm of the thickness of " ESPANEX " of Nippon Steel & Sumitomo Metal Corporation, copper foil (conductor), poly-
25 μm of the thickness of acid imide film)
Surface treatment: 3 mass % sulfuric acid treatments
Print process: silk-screen printing
Dried film thickness: 20 μm and 40 μm
Predrying: 80 DEG C, 20 minutes
Exposure: using ORC MANUFACTURING CO., LTD.DI ultraviolet exposure apparatus according " Mns60 ", (light source is high-pressure mercury
Lamp) with 100mJ/cm2Film is exposed
Development: 1 30 DEG C of mass % aqueous sodium carbonate temperature, injection pressure 0.2MPa, developing time 60 seconds
Solidify afterwards: 150 DEG C, 60 minutes
Evaluation
(1) sensitivity
By coated substrates, after twenty minutes, sensitometry stagewise exposure meter (Kodak is arranged in predrying on film at 80 DEG C
14 grades), it will be by sensitometry stagewise exposure meter with 100mJ/cm2The main peak of illumination wavelength is the ultraviolet light of 365nm, by
This obtains test film (dried film thickness is 20 μm).It is measured using the accumulative quantometer of ORC MANUFACTURING CO., LTD. above-mentioned
Irradiate light quantity.After ultraviolet exposure, used according to above-mentioned test film production process using the aqueous sodium carbonate of 1 mass %
The injection pressure of 0.2MPa develop within 60 seconds, indicates the part that exposed portion is not removed with digital (number of degrees).Number of degrees
It is bigger, indicate that photobehavior is the better.
(2) undercut
The section (40 μm of dried film thickness) of the remaining line of the exposure portion formed for the photomask via 200 μm of line interval, uses gold
Belong to microscope (Olympus Co., Ltd, STM6), measures its maximum width (a) and minimum widith (b), calculate its poor ((a)-
(b)), to measure undercut.
Show the results of the evaluation above-mentioned table 1.
As shown in above-mentioned table 1,2, passing through UV, visible light using 0.1 mass % ethyl diethylene glycol (DEG) acetate solution
The maximum value of absorbance when spectrophotometer is measured epoxide, 360nm or more is 0.250 or less, 310nm
Above and the maximum value of 360nm absorbance below is 0.020 or more and relative to the photoresist 100 containing carboxyl
Mass parts (solid component) contain the above-mentioned epoxide of about 25 mass parts and contain about 1 mass parts~about 4 mass parts light
In the Examples 1 to 8 of polymerization initiator, sensitivity is good, is 6 grades~8 grades, can inhibit undercut at 19 μm or less.In addition,
And with the maximum value of 320nm or more and 360nm above-mentioned absorbance below be 0.063 or more epoxide embodiment 1
~6 be 0.018 with the maximum value for only using 320nm or more and 360nm above-mentioned absorbance below epoxide implementation
Example 7,8 is compared, and undercut can be further suppressed.In addition, and with 340nm or more and the maximum of 360nm above-mentioned absorbance below
Value for 1.138 epoxide Examples 1 to 2 with and with 340nm or more and the maximum of 360nm above-mentioned absorbance below
The embodiment 3~6 for the epoxide that value is 0.021~0.030 is compared, and undercut can be further suppressed.
In addition, by the comparison of embodiment 1,3,5,7 and embodiment 2,4,6,8 it is found that if Photoepolymerizationinitiater initiater contains α-
Aminoalkyl-phenones class Photoepolymerizationinitiater initiater and oxime esters Photoepolymerizationinitiater initiater, and contain only oxime esters Photoepolymerizationinitiater initiater
Situation is compared, and undercut can be further suppressed.
On the other hand, containing about 10 mass relative to 100 mass parts of photoresist (solid component) containing carboxyl
In the Comparative Examples 1 and 2 of the epoxide with above-mentioned defined absorbance of part, fail to inhibit undercut.In addition, relative to
The comparative example 3 of Photoepolymerizationinitiater initiater of 100 mass parts of photoresist (solid component) containing carboxyl containing about 0.5 mass parts
In, fail to inhibit undercut.
Industrial availability
Even if photosensitive polymer combination of the invention on substrate due to forming thick (such as 40 μm or more thickness)
Cured coating film is also able to suppress the undercut of cured coating film, thus, for example the protective films such as solder resist formed in printing distributing board
It field, particularly photosensitive polymer combination is coated on the thickness of copper foil forms protective film than usual thick printing distributing board
Field, will have the dry film for making photosensitive polymer combination be coated on film made of film be applied to the thickness of copper foil than usual
Utility value is high in the field of thick substrate.
Claims (8)
1. a kind of photosensitive polymer combination, which is characterized in that contain the photoresist of (A) containing carboxyl, (B) epoxy compound
Object, (C) reactive diluent and (D) Photoepolymerizationinitiater initiater,
Using 0.1 mass % ethyl diethylene glycol (DEG) acetate solution, by ultraviolet-uisible spectrophotometer to (B) epoxy compound
When object is measured, the maximum value of the absorbance of the range of 360nm or more is 0.250 hereinafter, 310nm or more and 360nm or less
Range absorbance maximum value be 0.020 or more,
100 mass parts of photoresist relative to (A) containing carboxyl, (B) epoxy described in more than 15 mass parts
Compound, and contain (D) Photoepolymerizationinitiater initiater described in more than 0.6 mass parts.
2. photosensitive polymer combination according to claim 1, which is characterized in that (B) epoxide includes to make
With 0.1 mass % ethyl diethylene glycol (DEG) acetate solution by ultraviolet-uisible spectrophotometer measure when 320nm or more and 360nm with
Under range absorbance maximum value be 0.020 or more epoxide.
3. photosensitive polymer combination according to claim 1 or 2, which is characterized in that (B) epoxide includes
340nm or more and 360nm when being measured using 0.1 mass % ethyl diethylene glycol (DEG) acetate solution by ultraviolet-uisible spectrophotometer
The epoxide that the maximum value of the absorbance of range below is 1.0 or more.
4. photosensitive polymer combination according to any one of claim 1-3, which is characterized in that (B) epoxidation
Closing object includes selected from by 2 function naphthalene type epoxy resins, biphenyl type epoxy resin, xenol aralkyl-type epoxy resin and dimeric dibasic acid
At least one of the group that glycidyl ester type epoxy resin is constituted.
5. photosensitive polymer combination described in any one of -4 according to claim 1, which is characterized in that (D) photopolymerization
Initiator contains alpha-aminoalkyl phenyl ketone Photoepolymerizationinitiater initiater.
6. photosensitive polymer combination described in any one of -4 according to claim 1, which is characterized in that (D) photopolymerization
Initiator contains alpha-aminoalkyl phenyl ketone Photoepolymerizationinitiater initiater and oxime esters Photoepolymerizationinitiater initiater.
7. a kind of dry film, which is characterized in that have and be coated with photosensitive polymer combination of any of claims 1-6
The film made of film.
8. a kind of printing distributing board, which is characterized in that have photosensitive polymer combination of any of claims 1-6
Photocuring film.
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| JP6211780B2 (en) * | 2012-03-27 | 2017-10-11 | 太陽インキ製造株式会社 | Flame-retardant curable resin composition, dry film, flame-retardant coating and printed wiring board |
| JP6061576B2 (en) * | 2012-09-10 | 2017-01-18 | 株式会社タムラ製作所 | Photosensitive resin composition and printed wiring board having cured film of photosensitive resin composition |
| CN106662813B (en) * | 2014-06-12 | 2021-02-26 | 太阳油墨制造株式会社 | Curable resin composition, dry film, cured product, and printed wiring board |
| JP6172816B2 (en) * | 2015-11-02 | 2017-08-02 | 互応化学工業株式会社 | Photosensitive resin composition, dry film, printed wiring board, and method for producing photosensitive resin composition |
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