CN105849640B - The photosensitive resin composition of dry film photoresist - Google Patents
The photosensitive resin composition of dry film photoresist Download PDFInfo
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- CN105849640B CN105849640B CN201480071090.1A CN201480071090A CN105849640B CN 105849640 B CN105849640 B CN 105849640B CN 201480071090 A CN201480071090 A CN 201480071090A CN 105849640 B CN105849640 B CN 105849640B
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- dry film
- photosensitive resin
- resin composition
- epoxy resin
- film photoresist
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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
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
-
- 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
- G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
-
- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
- G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
- G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
- G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
Abstract
The present invention relates to a kind of photosensitive resin compositions that dry film photoresist is included, in more detail, it is related to a kind of while maintain excellent filament adherence and resolution ratio, it is also excellent to the acid resistance of etching solution, and it not only also can be improved photosensitive resin composition included in the dry film photoresist of quality and productivity in the preparation of PCB, the preparation of touch panel used using ITO as sensor and electrode etc..
Description
Technical field
The present invention relates to a kind of photosensitive resin compositions of dry film photoresist.
Background technique
Photosensitive resin composition is anti-with dry film photoresist (Dry Film Photoresist, DFR) or liquid photopolymerizable
Forms such as agent ink (Liquid Photoresist Ink) are lost to be mainly used for printed circuit board (Printed Circuit
Board, PCB) and lead frame (Lead Frame) etc. in.This photosensitive resin composition, on substrate with certain thickness into
After row coating, after selectively irradiating ultraviolet light to form desired circuit, using alkaline developer to be formed
The developing process of desired circuit carries out being etched substrate or using metal to baseplate part according to technique after development
Position carries out electroplating technique.
Recently, with the increase in demand to touch panel, using it is easy carry out patterned lithographic plate printing method come to
It is handled in electrode and the ITO of sensor etc., but existing positive type photosensitive material is liquid, therefore in the mistake being coated
It is lost in journey serious.In order to overcome this disadvantage, the care to dry film photoresist recently and demand are in increased trend.
Existing photosensitive resin composition usually by be dissolved in the binder polymer of aqueous alkali, cross-linkable monomer, pigment,
Photoepolymerizationinitiater initiater and solvent composition.It as needed can be containing for enhancing and the bonding force reinforcing agent of substrate bonding force, use
In the stabilizer of storage stability, for enhancing and the additives such as the dispersing agent of dispersibility of pigment.
This existing photosensitive resin composition is poly- as adhesive using the pure acrylic resin for being dissolved in aqueous alkali
Close object, therefore weak to the acid resistance of the ingredients such as hydrochloric acid, nitric acid of composition etching solution, thus it is bad there are process recovery ratio the problems such as.
On the other hand, although disclosing the epoxy for being reacted and being formed with acrylic acid using phenolic resin varnish type epoxy resin
The photosensitive resin composition (KR published patent the 2008-0014147th) of vinylester resin, but still there are resolution ratio reductions
The problem of.
Summary of the invention
The technical problems to be solved by the invention
The main purpose of the present invention is to provide it is a kind of maintain excellent filament adherence and resolution ratio while, to etching
Liquid has the photosensitive resin composition of excellent acid proof dry film photoresist.
Solve the mode of technical problem
To achieve the goals above, an embodiment of the invention provides a kind of photosensitive tree of dry film photoresist
Oil/fat composition, it is characterized in that, the photosensitive resin composition of the dry film photoresist contains the polymerization of alkali-developable adhesive
Object (A), Photoepolymerizationinitiater initiater (B) and photopolymerizable compound (C), the alkali-developable binder polymer (A) contain epoxy
It is acrylic resin modified.
A preferred embodiment of the present invention, it is characterized in that, the acid value of the epoxy modified acrylic resin be 100 to
250mg KOH/g, weight average molecular weight 35,000 to 100,000g/mol.
A preferred embodiment of the present invention, it is characterized in that, the epoxy modified acrylic resin is to make acrylic acid list
Body polymerize and after generating acrylate copolymer, in the presence of a catalyst to acrylate copolymer generated and epoxy resin
The product for carrying out ring-opening polymerisation and obtaining.
A preferred embodiment of the present invention, it is characterized in that, the epoxide equivalent of the epoxy resin be 180g/eq extremely
1500g/eq。
A preferred embodiment of the present invention, it is characterized in that, the epoxy resin is selected from bisphenol-type epoxy resin, phenolic aldehyde
Type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, linear aliphatic epoxy resins,
One or more of alicyclic epoxy resin and biphenyl type epoxy resin.
A preferred embodiment of the present invention, it is characterized in that, the photosensitive resin composition contains 20 to 80 weight %
Alkali-developable binder polymer (A), 2 to 10 weight % Photoepolymerizationinitiater initiater (B) and 10 to 70 weight % photopolymerization
Property compound (C).
The effect of invention
The photosensitive resin composition of dry film photoresist according to the present invention, maintain excellent filament adherence and
It is also excellent to the acid resistance of etching solution while resolution ratio, not only in the preparation of PCB, using ITO as sensor and electrode
Also quality and productivity be can be improved in the preparation of the touch panel used etc..
Specific embodiment
Whole technology as used in this specification and scientific term in the case where being defined not otherwise, tool
Have and those skilled in the art's usually meaning equivalent in meaning to understand.Nomenclature used in this specification is generally this
Usually used naming method known to field.
In description of the invention entirety, when using the statement of certain a part of certain ingredient of "comprising", not special
In the case where indicating opposite to that record, be not offered as exclude other compositions, but indicate can further include other at
Point.
Indicate that the term of degree, such as the terms such as " about ", " actually " indicate involved by it used in this specification
The meaning on, when intrinsic preparation and substance allowable error are disclosed, as meaning identical as the numerical value or close to the numerical value
Think, is that cankered infringer is undeservedly related to correct or absolute numerical value using for understanding the present invention in order to prevent
Disclosure.
The present invention relates to a kind of photosensitive resin compositions of dry film photoresist, it is characterized in that, the dry film is photic anti-
The photosensitive resin composition of erosion agent contains alkali-developable binder polymer (A), Photoepolymerizationinitiater initiater (B) and optical polymerism
It closes object (C), the alkali-developable binder polymer (A) contains epoxy modified acrylic resin.
The photosensitive resin composition of dry film photoresist according to the present invention, due to alkali-developable binder polymer
(A) contain epoxy modified acrylic resin in, therefore in the filament adherence and resolution for maintaining excellent dry film photoresist
While rate, not only there is excellent acid resistance to etching solution, but also needing to there is other acid acid proof all put down
It can be used in plate printing technology.
In the following, being illustrated in further detail to the present invention.
Alkali-developable binder polymer (A)
In photosensitive resin composition, since alkali-developable binder polymer is according to their ingredient, structure, gamma transition
Temperature, molecular weight, acid value etc. generate very the physical property of photoresist to determine the physical property of photoresist
It is big to influence.
Especially, generally mainly make in alkali-developable binder polymer used in common negative type photoresist
With pure acrylic resin, and this acrylic adhesives polymer is to the acidproof of the ingredients such as hydrochloric acid, the nitric acid of composition etching solution
Property is weak, therefore causes many problems in the etch process.
For this purpose, the present invention confirmed in the polymer, by chemical resistance as photoresist acid proof method is improved
It is excellent epoxy-modified in the case where acrylic acid, there is excellent acid resistance to etching solution, and circuit adherence is also excellent
It is different, it is easy to adjust coating mobility, and then complete the present invention.
Epoxy modified acrylic resin according to the present invention are as follows: polymerize in acrylic monomers and generate acroleic acid polymerization
After object, acrylate copolymer generated and epoxy resin carry out ring-opening polymerisation in the presence of a catalyst, and then make epoxy resin
The product for being grafted on (grafting) to acrylate copolymer and obtaining.At this point, the polymerization of the acrylic monomers can be
It is carried out 1 to 10 hour at 40 to 120 DEG C, the ring-opening polymerisation can carry out 1 to 8 hour at 60 to 100 DEG C, but not limit
In this.As long as acrylic resin can be modified as to the method and condition well-known in the art of epoxy group, can be used.
That is, " epoxy-modified " refers to be grafted on acrylate copolymer in epoxy modified acrylic resin of the invention
(grafting) meaning of epoxy resin, it is anti-with acrylic monomers and epoxy resin are merely synthesized (synthesis)
Answer difference.
In addition, the content of the acrylic monomers and epoxy resin is than the weight ratio for 70~95:5~30, it is upper exceeding
In the case where stating content ratio, the characteristic of epoxy resin will not exhibit, or make photoresist because of excessive epoxy resin
Oxidant layer is excessively soft, and then the problem of can not being coated or being layered can occur.
In addition, catalyst used in the ring-opening polymerisation, as long as can be used for the catalyst of epoxy ring opening reaction,
It can use without limitation.Specific enumerable zinc octoate, tin octoate, cobalt octoate etc..Its additive amount is with reactant total weight
It can be 0.01 to 5 weight %.
The acrylic monomers can be enumerated such as styrene, methyl methacrylate, methyl acrylate, ethyl acrylate, first
Base ethyl acrylate, 2- ethylhexyl acrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, third
Olefin(e) acid isobutyl ester, n-BMA, Isobutyl methacrylate, the just own ester of methacrylic acid, lauryl
Ester, acrylic acid, methacrylic acid, 2- hydroxyethyl methacrylate, 2- hydroxy-ethyl acrylate, hydroxypropyl acrylate, acrylic acid hydroxyl
Butyl ester etc..Can also by they respectively using or be used in mixed way.
In addition, can enumerate as epoxy resin such as bisphenol-type epoxy resin, phenolic resin varnish type epoxy resin, shrink are sweet
Oily ester type epoxy resin, glycidyl amine type epoxy resin, linear aliphatic epoxy resins, alicyclic epoxy resin and biphenyl type
Epoxy resin etc..In terms of operability and chemical resistance, bisphenol-type epoxy resin preferably wherein.
The bisphenol-type epoxy resin can pass through bisphenols and epoxychloropropane, Alpha-Methyl epoxychloropropane etc. and halogenation
The reaction of epoxides and obtain.
The bisphenols can enumerate as phenol or 2,6- dihalide phenol and formaldehyde, acetaldehyde, acetone, acetophenone, cyclohexanone,
The aldehydes such as Benzophenone, or with the reaction product of ketone and the oxidation product generated according to the peracidity of dihydroxy benzenes thioether,
The esterification reaction product etc. of quinhydrones.In these bisphenol-type epoxy resins, especially it is widely used and preferably as bisphenols
Bisphenol-A, bisphenol S, Bisphenol F or using they hydrogenation products and the bisphenol-type epoxy resin that obtains.
In addition, the epoxide equivalent of the epoxy resin preferred 180g/eq to 1500g/eq.Use epoxide equivalent deficiency
In the case where the epoxy resin of 180g/eq, resin can be made tacky, it is simultaneous in the case where the epoxy resin for using more than 1500g/eg
Capacitive can reduce, and then will lead to opaque, can generate when serious and mutually separate.
The glass transition temperature of the acrylate copolymer as made of the polymerizable acrylic monomer is 40 to 150 DEG C, if
When the glass transition temperature of acrylate copolymer is lower than 40 DEG C, then after coating, reduced with the drying capacity of heated-air drying, and meeting
It is tacky, and then be not suitable for using, when glass transition temperature is higher than 150 DEG C, then film becomes fragile (brittle), and it is frangible, therefore
It is unsuitable preferred.
The acid value of epoxy modified acrylic resin obtained is 100 to 250mg KOH/g according to the method described above, the epoxy
In the case that acrylic resin modified acid value is less than 100mg KOH/g, when carrying out development and stripping technology, with aqueous slkali
Reaction time can be elongated, and then can cause the problem of reducing yield.In the case where more than 250mg KOH/g, in storage group
Can corrode storage container when closing object, or oxidation, reduction reaction can occur etc., also, because with the contact of substrate (substrate)
And in producing bubbles inside, and then while can occur bad, development and peeling rate are too fast, and then exist and be difficult to adapt in behaviour
The problem of property made.
The weight average molecular weight of the epoxy modified acrylic resin is 35,000 to 100,000g/mol, and weight average molecular weight is low
In the case where 35,000g/mol, wandering property can become by force, and then be not suitable for use in film, and there are acid resistances significantly
The problem of reduction.In the case where 100,000g/mol, viscosity can rise, and then substantially reduce mobility, exist and be difficult to
The problem of preparing uniform coating.
In alkali-developable binder polymer according to the present invention, in addition to can contain epoxy modified acrylic resin it
Outside, acrylate copolymer can also further be contained.The acrylate copolymer is will be selected from by methyl acrylate, methyl
Methyl acrylate, ethyl acrylate, methyl methacrylate, butyl acrylate, butyl methacrylate, acrylic acid, methyl-prop
Olefin(e) acid, 2- hydroxy-ethyl acrylate, 2- hydroxyethyl methacrylate, 2- hydroxypropyl acrylate, 2- hydroxy propyl methacrylate, propylene
The two or more monomers in linear acrylic macromolecule that amide, Methacrylamide, styrene, α-methylstyrene synthesize
The co-polypropylene acid macromolecule obtained by copolymerization.
In addition, alkali-developable binder polymer according to the present invention with photosensitive resin composition total weight contain 20 to
80 weight %.The content of the alkali-developable binder polymer within the above range in the case where, after the circuitry is formed, can
Obtain the effect for enhancing acid resistance and filament adhesion force.
Photoepolymerizationinitiater initiater (B)
Photoepolymerizationinitiater initiater contained in the photosensitive resin composition of dry film photoresist of the invention is with UV
And other radiation (radiation) induce the substance of the chain reaction of photopolymerization monomer, in consolidating for dry film photoresist
It is played an important role in change.
It is derivative that compound as the Photoepolymerizationinitiater initiater can enumerate such as 2-methylanthraquinone, 2- ethyl hydrazine Anthraquinones
Object, benzoin methyl ether, diphenylmethanone, phenanthrenequione, 4, the Benzoin derivatives such as 4 '-bis--(dimethylamino) benzophenone.
Further, it is also possible to which 2,2- bis- (2- chlorphenyls) -4,4 ' -5,5 '-tetraphenyl bisglyoxaline, 1- hydroxy-cyclohexyl will be selected from
Phenyl ketone, 2,2- dimethoxy-1,2- diphenylethane-1- ketone, 2- methyl-1-[4- (methyl thio) phenyl]-2- morpholine
For propane -1- ketone, 2- benzyl -2- dimethylamino -1- [4- morphlinophenyl] butane -1- ketone, 2- hydroxy-2-methyl -1- phenyl
Propane -1- ketone, 2,4,6- trimethyl benzoyl diphenyl base phosphine oxide, 1- [4- (2- hydroxymethoxy) phenyl] -2- hydroxyl -2-
Methylpropane -1- ketone, 2,4- diethyl thioxanthone, 2-chlorothioxanthone, 2,4- dimethyl thioxanthone, 3,3- dimethyl -4- methoxy
The chloro- 4- propoxythioxanthone of base diphenylmethanone, diphenylmethanone, 1-, 1- (4- isopropyl phenyl) 2- hydroxy-2-methyl third
Alkane -1- ketone, 1- (4- dodecylphenyl) -2- hydroxy-2-methyl propane -1- ketone, 4- benzoyl -4 '-methyl dimethoxy base sulphur
Ether, 4- dimethylaminobenzoic acid, 4- dimethylaminobenzoic acid methyl esters, ethyl 4-dimethylaminobenzoate, 4- dimethyl
Butyl aminobenzoate, 4- dimethylaminobenzoic acid 2- ethylhexyl, 4- dimethylaminobenzoic acid 2- isopentyl ester, 2,2- bis-
Acetophenone, benzyl ketone dimethylacetal, benzyl ketone 'beta '-methoxy diethyl ketal, 1- phenyl -1,2- propyl dioxime-o,
O '-(2- carbonyl) ethyoxyl ether, methyl o-benzoylbenzoate, bis- [4- dimethylaminophenyl] ketones, 4,4 '-bis- (diethyls
Base amino) Benzophenone, 4,4 '-dichloro Benzophenones, benzil, styrax, methoxyl group styrax, ethoxy ethyl perfume, isopropyl oxygen
Base styrax, n-butoxy styrax, isobutoxy styrax, three-level butoxy styrax, to dimethylamino benzoylformaldoxime, right
Three-level butyl trichloroacetophenone, to three-level butyl dichloroacetophenone, thioxanthones, 2- methyl thioxanthones, 2-isopropylthioxanthone, two
Benzo ring heptane, α, the compound in α,α-dichloro-4-phenoxy acetophenone, 4- dimethylaminobenzoic acid pentyl ester is as photopolymerization
Initiator uses, and but not limited to this.
The content of the Photoepolymerizationinitiater initiater contains 2 to 10 weight % with photosensitive resin composition total weight.The light
The content of polymerization initiator within the above range when, sufficient susceptibility can be obtained, in exposing operation, can reduce because expose
Physical property deviation caused by light device or other external conditions.
Photopolymerizable compound (C)
Olefinically unsaturated compounds have polyfunctional monomer and monofunctional monomer, as polyfunctional monomer, there are ethylene glycol
Dimethylacrylate (ethylene glycol dimethacrylate), dimethacrylate diethylene glycol (DEG) ester
(diethylene glycol dimethacrylate), tetraethylene glycol dimethacrylate (tetraethylene glycol
Dimethacrylate), dimethacrylate (propylene glycol dimethacrylate), poly- the third two
Alcohol dimethylacrylate (polypropylene glycol dimethacrylate), butanediol dimethylacrylate
(butylene glycol dimethacrylate), dimethyl diacrylate peopentyl ester (neopentyl glycol
Dimethacrylate), 1,6-HD dimethylacrylate (1,6-hexane glycol dimethacrylate), three
Methylolpropane trimethacrylate (trimethyolpropane trimethacrylate), dimethyl allene acid glycerol
Ester (glycerin dimethacrylate), dimethyl pentaerythritol acrylate (pentaerythritol
Dimethacrylate), pentaerythritol acrylate trimethyl (pentaerythritol trimethacrylate), two seasons
Penta tetrol pentamethacrylate (dipentaerythritol pentamethacrylate), bis- (the 4- methacryls of 2,2-
Oxygroup diethoxy phenyl) propane (2,2-bis (4-methacryloxydiethoxyphenyl) propane), 2- hydroxyl -3-
Methacryloyloxypropyl methyl acrylate (2-hydroxy-3-methacryloyloxypropyl
Methacrylate), ethylene glycol diglycidylether dimethylacrylate (ethylene glycol diglycidyl
Ether dimethacrylate), diethylene glycol diglycidyl glycerin ether dimethylacrylate (diethylene glycol
Diglycidyl ether dimethacrylate), phthalic acid diglycidyl ether dimethylacrylate
(phthalic acid diglycidyl ester dimethacrylate), polyglycidyl ether polymethyl acid glycerol
Ester (glycerin polyglycidyl ether polymethacrylate) etc..
It could be used with the monofunctional monomer of appropriate amount with polyfunctional monomer.As monofunctional monomer, such as there is first
Base acrylic acid 2- hydroxyl ethyl ester (2-hydroxyethyl methacrylate), methacrylic acid 2- hydroxypropyl acrylate (2-
Hydroxypropyl methacrylate), methacrylic acid 2- hydroxy butyl ester (2-hydroxybutyl methacrylate),
2- phenoxy group -2- hydroxypropyl methacrylate (2-phenoxy-2-hydroxypropyl methacrylate), 2- methyl
Acryloxy -2- phthalic acid hydroxypropyl acrylate (2-methacryloyloxy-2-hydroxypropyl phthalate), 3-
Chloro- 2- hydroxypropyl methacrylate (3-chloro-2-hydroxypropyl methacrylate), monomethacrylate are sweet
Grease (glycerin monomethacrylate), 2- first acryloyl-oxyethyl acid phosphoric acid ester (2-
Methacryloyloxyethyl acid phosphate), the methyl-prop of phthalic acid (phthalic acid) derivative
Olefin(e) acid ester, N- methylol methacrylamide (N-methylol methacrylamide), 2,2 '-bis--[4- (methacryls
Oxygroup-polyethoxy) phenyl] propane, polyethylene glycol polypropylene glycol dimethacrylate etc..
The photopolymerizable compound can contain 10 to 70 weight % in photosensitive resin composition.The optical polymerism
The content of compound within the above range when, have the effect of strengthening lightsensitivity and the circuits physical property such as adhesion force and resolution ratio.
Solvent and other additives (D)
The solvent of photosensitive resin composition of the invention, usually can be in methyl ethyl ketone (MEK), methanol, tetrahydrofuran
(THF), toluene, select in acetone to use, to the solvent, there is no particular limitation, and content still can cause according to photopolymerization
The content of agent, alkali-developable binder polymer and photopolymerizable compound is adjusted.
In addition, photosensitive resin composition of the invention can also include other additives as needed, as other additions
Dibutyl phthalate, the dibutyl phthalate (DHP), neighbour of the phthalic acid ester form as plasticizer can be used in agent
Dioctyl phthalate, diallyl phthalate；Triethylene glycol diacetate, two vinegar of tetraethylene glycol of glycol ester form
Acid esters；Para toluene sulfonamide, benzsulfamide, the nbutylbenzenesulfonamide of sour amide form；Triphenyl phosphate etc..
In order to improve the treatability of photosensitive resin composition of the invention, leuco dye or coloring material can also be added.
The leuco dye can enumerate three (4- dimethylamino -2- aminomethyl phenyl) methane, three (- 2 methylbenzenes of 4- dimethylamino
Base) methane, fluoran dyestuff etc..Wherein, using colorless crystal violet, because contrast is good and preferred.Containing
In the case where having leuco dye, content contains 0.1 to 10 weight % preferably in photosensitive resin composition.From the table of contrast
From the viewpoint of reaching, preferably 0.1 weight % or more, from the viewpoint of maintaining storage stability, preferably 10 weight % or less.
As coloring material, toluenesulfonic acid monohydrate, basic fuchsin, phthalocyanine green, auramine alkali, para product can be enumerated
Red, crystal violet, methyl orange, Nile blue 2B, Victoria blue, peacock green, diamond green, alkali blue 20 etc..Contain above-mentioned coloring object
In the case where matter, content contains 0.001 to 2 weight % preferably in photosensitive resin composition.More than 0.001 weight %
Have the effect of improving treatability have the effect of maintaining storage stability under 2 weight % contents below under content.
Furthermore, it is possible to further containing as the thermal polymerization preventing agent of other additives, dyestuff, colour-changing agent
(discoloring agent), adhesion force promotor etc..
In the present invention, the photosensitive resin composition formed as described above can be prepared into the light of dry film photoresist
Photosensitive resin composition, on the common base film such as polyethylene terephthalate, using common coating method, with 5 to
After 200 μm of thickness coating photosensitive resin layer, makes it dry, can use poly- second in the upper surface of the photosensitive resin layer of the drying
The common protective film such as alkene is laminated, and then dry film is made.Thus obtained dry film is exposed, is developed, is then adopted
It is carried out with the method for evaluating each physical property.
In the following, being illustrated to the preferred embodiment of the present invention and comparative example.But following embodiments are only of the invention
Preferred embodiment, the present invention is not limited to following embodiments.
[preparation example 1 to 3]
Thermometer, mechanical stirrer (mechanical stirrer) and reflux unit are installed on four mouthfuls of round bottom beakers
Afterwards, inside using nitrogen purification beaker.Using addition 90g methyl ethyl ketone (Methyl Ethyl in the purified beaker of nitrogen
Ketone, MEK) and 10g propylene glycol monomethyl ether acetate (Propylene Glycol Monomehtyl Ether Acetate,
PGMEA it after), is added 1.5g azodiisobutyronitrile (azobisisobutyronitrile, AIBN), makes it completely dissolved.Herein
Acrylic monomers recorded in table 1 is added, polymerize 6 hours at 80 DEG C, and then obtains acrylate copolymer.In above-mentioned generation
15g bisphenol A type epoxy resin (epoxide equivalent 450g/eq, YD-011, national capital chemistry) is added in acrylate copolymer and 0.5g is pungent
Sour zinc (Aldrich), ring-opening reaction 6 hours at 80 DEG C, and then alkali-developable binder polymer is made.
[preparation example 4 and 5]
After mechanical stirrer, thermometer and reflux unit are installed on four mouthfuls of round bottom beakers, beaker is purified using nitrogen
It is internal.0.8g AIBN is added in 90g MEK and 10g PGMEA, makes it completely dissolved.Then 100g recorded in table 1 is mono-
Body is added in beaker, is polymerize 6 hours at 80 DEG C.
It is measured using physical property of the following methods to binder polymer obtained in the preparation example, the results are shown in
In table 1.
(1) acid value measuring
1g binder polymer is sampled, mixed solvent (methanol (MeOH) 20%, the acetone of 50ml are dissolved in
(Acetone) in 80%), then 2 drop 1%- phenolphthalein reagent of addition is titrated, and then measure acid value with 0.1N-KOH.
(2) molecular weight determination
The weight to be converted with polystyrene is measured according to gel permeation chromatography (GPC) (water (Waters): Waters707)
Average molecular weight (Mw) and number-average molecular weight (Mn).Binder polymer obtained in above-mentioned preparation example is dissolved in tetrahydrofuran
In, so that concentration is become 4000ppm, then 100 μ l are injected into GPC.The mobile phase of GPC uses tetrahydrofuran, with 1.0ml/
The flow velocity of minute flows into, and analysis is carried out at 35 DEG C.Waters HR-05,1,2,4E this four are connected in series and are used as layer
Analyse tubing string.It is measured at 35 DEG C using RI and PAD Detector detector.At this point, by the weight average molecular weight of measurement
PDI (polydispersity index) is calculated divided by number-average molecular weight.
(3) glass transition temperature measures
In Differential Scanning Calorimeter analyzer (Differential Scanning Calorimeter, DSC) (Perkin-
Elmer company, DSC-7) in relatively control (reference) adhesive composition.Temperature is set at 20 DEG C and maintains 15 points
Zhong Hou is measured after being warming up to 200 DEG C with the heating rate of 1 DEG C/min.
[table 1]
| Preparation example 1 | Preparation example 2 | Preparation example 3 | Preparation example 4 | Preparation example 5 | |
| Monomer 1: butyl acrylate | - | - | - | - | 10g |
| Monomer 2: methacrylic acid | 25g | 25g | 25g | 25g | 25g |
| Monomer 3: methyl methacrylate | 40g | 30g | 15g | 45g | 35g |
| Monomer 4: styrene | 30g | 30g | 30g | 30g | 30g |
| Bisphenol A type epoxy resin | 5g | 15g | 30g | - | - |
| Acid value (mg KOH/g) | 156 | 145 | 134 | 160 | 165 |
| Weight average molecular weight (g/mol) | 51,000 | 54,500 | 58,500 | 55,000 | 55,500 |
| Glass transition temperature (DEG C) | - | - | - | 130 | 90 |
[embodiment 1 to 3 and comparative example 1 and 2]
The photosensitive resin composition of dry film photoresist is prepared and applied according to composition shown in following table 2
Cloth, and then evaluated.Firstly, being dissolved in Photoepolymerizationinitiater initiater class in the methyl ethyl ketone (MEK) as solvent, then, light is added
The alkali-developable binder polymer of polymerizable compound and preparation example, using mechanical agitator mixing about 1 hour or so, in turn
Obtain photosensitive resin composition.The PET that the photosensitive resin composition of above-mentioned acquisition is coated on 20 μm using spreading rod (bar) is thin
On film.It is dried using photosensitive resin composition layer of the hot-blast oven to coating, drying temperature at this time is 80 DEG C, when dry
Between be 5 minutes, it is dry after photosensitive resin composition layer with a thickness of 20 μm.Drying will be completed using protective film (polyethylene)
Film be laminated on photosensitive resin layer.
[table 2]
To using under the photosensitive resin composition according to made from above-mentioned composition and then dry film photoresist obtained implementation
State technique.
<lamination>
With basal plate preheating roll temperature be 120 DEG C, lamination roll temperature is 115 DEG C, roller pressure 4.0kgf/cm2, roller speed be
The condition of 2.5min/m is laminated dry film photoresist.In order to confirm circuit characteristic, NITTO DENKO company is used
Ito thin film is as material, in order to implement ageing of metal (metal aging), implements aging in 30 minutes at 120 DEG C.
<development>
On ito thin film, using the light shield for evaluating circuit, and Perkin-ElmerTM OB7120 (directional light is utilized
Exposure machine), after irradiating ultraviolet light respectively with dry film photoresist of 16 grades of the light exposure to lamination in 41 grades of stages, place
20 minutes, then by 30 DEG C of 1.0wt%Na2CO3Aqueous solution is with 1.5kgf/cm2Pressure sprayed and developed.Measure ITO
The time (minimum developing time) that the unexposed developed liquid of dry film photoresist completely removes on film, and its result is remembered
It is loaded in table 3.
<circuit characteristic evaluation>
Circuit characteristic evaluation is after being developed with 2 times of minimum developing times, to be evaluated using electron microscope.This
When, filament adhesion force after development, to retain the minimum feature for having independent resist, utilizes ZEISS AXIOPHOT
Microscope is measured, and resolution ratio is that the ratio that the space between circuit line and circuit line is set as 1:1 is measured
Value, is measured using ZEISS AXIOPHOT Microscope.Its result is recorded in table 3.
<acid resistance evaluation>
The ito thin film for completing development is put into the cup equipped with ITO etching solution, places after a certain period of time, confirms remaining
Minimum pattern (pattern), and be recorded in table 4.
[table 3]
As shown in table 3, embodiment 1 to 3 is able to confirm that compared with comparative example 1 and 2, maintains the filament adherence of similar level
Power and resolution ratio, also, the minimum developing time of comparative example 1 and 2 is too fast less than 10 seconds, and therefore, it is difficult to be suitable for operability.
[table 4]
As shown in table 4, it is able to confirm that embodiment 1 to 3 compared with comparative example 1 and 2, has excellent acid resistance.
To simple deformation of the invention and change it is that those skilled in the art can be easy implementation, therefore above-mentioned
Deformation or change are all contained in the scope of the present invention.
[industrial applicibility]
The photosensitive resin composition of dry film photoresist according to the present invention has excellent filament adherence and divides
It is also excellent to the acid resistance of etching solution while resolution, can be applied to printed circuit board (PCB) preparation and using ITO as
In the process industries such as the touch panel that sensor and electrode use, quality and productivity can be improved.
Claims (5)
1. a kind of photosensitive resin composition of dry film photoresist, it is characterized in that,
The photosensitive resin composition of the dry film photoresist contains: alkali-developable binder polymer (A), photopolymerization cause
Agent (B) and photopolymerizable compound (C),
The alkali-developable binder polymer (A) contains epoxy modified acrylic resin,
The epoxy modified acrylic resin is after polymerizeing acrylic monomers and generating acrylate copolymer, to giving birth to
At acrylate copolymer and epoxy resin carry out ring-opening polymerisation in the presence of a catalyst, and then make epoxy resin graft to propylene
The product obtained on acid polymer.
2. the photosensitive resin composition of dry film photoresist according to claim 1, it is characterized in that,
The acid value of the epoxy modified acrylic resin is 100 to 250mg KOH/g, weight average molecular weight 35,000 to 100,
000g/mol。
3. the photosensitive resin composition of dry film photoresist according to claim 1, it is characterized in that,
The epoxide equivalent of the epoxy resin is 180g/eq to 1500g/eq.
4. the photosensitive resin composition of dry film photoresist according to claim 1, it is characterized in that,
The epoxy resin is selected from bisphenol-type epoxy resin, phenolic resin varnish type epoxy resin, glycidyl ester type epoxy resin, contracting
One of water glyceramine type epoxy resin, linear aliphatic epoxy resins, alicyclic epoxy resin and biphenyl type epoxy resin
More than.
5. the photosensitive resin composition of dry film photoresist according to claim 1, it is characterized in that,
The photosensitive resin composition contains the alkali-developable binder polymer (A) of 20 to 80 weight %, 2 to 10 weight %
The photopolymerizable compound (C) of Photoepolymerizationinitiater initiater (B) and 10 to 70 weight %.
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| KR20130162183 | 2013-12-24 | ||
| KR10-2013-0162183 | 2013-12-24 | ||
| KR10-2014-0184335 | 2014-12-19 | ||
| KR1020140184335A KR101692003B1 (en) | 2013-12-24 | 2014-12-19 | Photosensitive Resin Composition for Dry Film Photoresist |
| PCT/KR2014/012620 WO2015099371A1 (en) | 2013-12-24 | 2014-12-22 | Photosensitive resin composition for dry film photoresist |
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| CN111123647B (en) * | 2020-01-14 | 2023-04-25 | 广东省石油与精细化工研究院 | Dry film photoresist and application thereof |
| CN115368609A (en) * | 2022-08-09 | 2022-11-22 | 浙江铭天电子新材料有限公司 | Preparation method of UV (ultraviolet) cured PCB (printed Circuit Board) dry film for copper-clad plate photoetching |
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| KR20060036577A (en) * | 2004-10-26 | 2006-05-02 | 주식회사 코오롱 | Photosensitive resin composition and dry-film photoresist using it |
| CN101538348A (en) * | 2008-03-18 | 2009-09-23 | 日本化药株式会社 | Active energy ray solidification type resin composition using reactivity compound with fire retardance and condensate thereof |
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| TW200519535A (en) * | 2003-11-27 | 2005-06-16 | Taiyo Ink Mfg Co Ltd | Hardenable resin composition, hardened body thereof, and printed circuit board |
| KR101052764B1 (en) * | 2004-06-08 | 2011-07-29 | 코오롱인더스트리 주식회사 | Photosensitive resin composition for dry film photoresist suitable for forming TFT pattern |
| JP4631808B2 (en) * | 2006-06-08 | 2011-02-16 | 住友化学株式会社 | Colored photosensitive resin composition |
| KR101361753B1 (en) * | 2010-03-22 | 2014-02-12 | 주식회사 엘지화학 | Photo-curable and thermo-curable resin composition, and dry film solder resist |
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| CN101538348A (en) * | 2008-03-18 | 2009-09-23 | 日本化药株式会社 | Active energy ray solidification type resin composition using reactivity compound with fire retardance and condensate thereof |
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