CN105849640A - Photosensitive resin composition for dry film photoresist - Google Patents
Photosensitive resin composition for dry film photoresist Download PDFInfo
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- CN105849640A CN105849640A CN201480071090.1A CN201480071090A CN105849640A CN 105849640 A CN105849640 A CN 105849640A CN 201480071090 A CN201480071090 A CN 201480071090A CN 105849640 A CN105849640 A CN 105849640A
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- resin composition
- photosensitive resin
- dry film
- film photoresist
- epoxy resin
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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
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- Engineering & Computer Science (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Engineering & Computer Science (AREA)
- Theoretical Computer Science (AREA)
- Architecture (AREA)
- Structural Engineering (AREA)
- Human Computer Interaction (AREA)
- Materials For Photolithography (AREA)
- Manufacturing Of Printed Circuit Boards (AREA)
Abstract
The present invention relates to a photosensitive resin composition which is included in a dry film photoresist and, more specifically, to a photosensitive resin composition which is included a dry film photoresist, capable of improving quality and productivity in the manufacture of PCBs and touch panels and the like that use ITO for sensors and electrodes, since the composition has superior acid-resistance against an etching solution even while maintaining excellent fine wire adhesion and resolution.
Description
Technical field
The present invention relates to the photosensitive resin composition of a kind of dry film photoresist.
Background technology
Photosensitive resin composition is with dry film photoresist (Dry Film Photoresist, DFR) or liquid light
Cause the forms such as resist ink (Liquid Photoresist Ink) and be mainly used for printed circuit board (PCB) (Printed
Circuit Board, PCB) and lead frame (Lead Frame) etc. in.This photosensitive resin composition,
After substrate is coated with certain thickness, optionally irradiate to form desired circuit
After ultraviolet, alkaline developer is utilized to carry out being formed the developing process of desired circuit, after development,
Carry out according to technique substrate being etched or utilizing metal that substrate position is carried out electroplating technique.
Recently, along with the increase in demand to contact panel, the offset printing side easily carrying out patterning is used
ITO etc. for electrode and sensor is processed by method, but existing positive type photosensitive material is liquid
Shape, therefore during being coated, loss is serious.In order to overcome this shortcoming, recently to dry film light
Cause care and the demand trend in increase of resist.
Existing photosensitive resin composition is generally by being dissolved in the binder polymer of aqueous alkali, bridging property list
Body, pigment, Photoepolymerizationinitiater initiater and solvent composition.As required can be containing viscous with substrate for strengthening
Bonding force reinforcing agent with joint efforts, the stabilizer for storage stability, the dispersibility for enhancing with pigment
The additive such as dispersant.
This existing photosensitive resin composition uses the pure acrylic resin being dissolved in aqueous alkali to be used as gluing
Binder polymer, therefore weak to the acid resistance of the compositions such as the composition hydrochloric acid of etching solution, nitric acid, therefore exist
The problems such as process recovery ratio is the best.
On the other hand, although disclose use phenolic resin varnish type epoxy resin and carry out reacting and shape with acrylic acid
The photosensitive resin composition (KR published patent the 2008-0014147th) of the oxireme ester resin become,
But still there is the problem that resolution reduces.
Summary of the invention
Invent technical problem to be solved
Present invention is primarily targeted at provides a kind of and maintains the same of excellent fine rule adherence and resolution
Time, etching solution is had the photosensitive resin composition of the acid proof dry film photoresist of excellence.
Solve the mode of technical problem
To achieve these goals, an embodiment of the invention provides a kind of dry film photoresist to use
Photosensitive resin composition, it is characterized by, the photosensitive resin composition of described dry film photoresist contains
There are alkali-developable binder polymer (A), Photoepolymerizationinitiater initiater (B) and photopolymerizable compound (C),
Described alkali-developable binder polymer (A) contains epoxy modified acrylic resin.
A preferred embodiment of the present invention, is characterized by, the acid of described epoxy modified acrylic resin
Value is 100 to 250mg KOH/g, and weight average molecular weight is 35,000 to 100,000g/mol.
A preferred embodiment of the present invention, is characterized by, described epoxy modified acrylic resin is,
Make acrylic monomers carry out being polymerized and after generating acrylate copolymer, to the acrylate copolymer generated with
The product that epoxy resin carries out ring-opening polymerisation in the presence of a catalyst and obtains.
A preferred embodiment of the present invention, is characterized by, the epoxide equivalent of described epoxy resin is 180
G/eq to 1500g/eq.
A preferred embodiment of the present invention, is characterized by, described epoxy resin is selected from biphenol type epoxy
Resin, phenolic resin varnish type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine epoxy tree
More than one in fat, linear aliphatic epoxy resins, alicyclic epoxy resin and biphenyl type epoxy resin.
A preferred embodiment of the present invention, is characterized by, described photosensitive resin composition contain 20 to
The alkali-developable binder polymer (A) of 80 weight %, the Photoepolymerizationinitiater initiater (B) of 2 to 10 weight %
And 10 to 70 photopolymerizable compound (C) of weight %.
The effect of invention
The photosensitive resin composition of the dry film photoresist according to the present invention, at the fine rule maintaining excellence
While adherence and resolution, the most excellent to the acid resistance of etching solution, not only in the preparation of PCB, with
The preparation of the contact panel etc. that ITO uses as sensor and electrode also is able to improve quality and production
Rate.
Detailed description of the invention
Whole technology as used in this specification and scientific terminology are in the feelings being defined not otherwise
Under condition, there is the to understand equivalent in meaning meaning usual with those skilled in the art.In this specification
The nomenclature used is generally normally used naming method known in the art.
In description of the invention entirety, when using the statement of certain part " comprising " certain composition,
In the case of not specializing opposite to that record, it is not offered as getting rid of other compositions, but table
Show and can comprise other compositions further.
The term of expression degree used in this specification, such as " about ", the term such as " actually " represents
In the meaning that it is involved, when intrinsic preparation and material allowable error are disclosed, it is used as and this number
Be worth identical or close to this numerical value the meaning, be in order to prevent cankered infringer utilize undeservedly for
Understand that the present invention relates to the disclosure of correct or absolute numerical value.
The present invention relates to the photosensitive resin composition of a kind of dry film photoresist, it is characterized by, this is done
The photosensitive resin composition of film photoresist contains alkali-developable binder polymer (A), photopolymerization
Initiator (B) and photopolymerizable compound (C), described alkali-developable binder polymer (A) is contained
Epoxy modified acrylic resin.
The photosensitive resin composition of the dry film photoresist according to the present invention, owing to alkali-developable bonds
Containing epoxy modified acrylic resin in agent polymer (A), therefore at the dry film photoresist maintaining excellence
While the fine rule adherence of agent and resolution, not only etching solution is had the acid resistance of excellence, Er Qie
Need other acid is had in acid proof all of lithography process and all can use.
Below, the present invention is illustrated in further detail.
Alkali-developable binder polymer (A)
In photosensitive resin composition, due to alkali-developable binder polymer according to their composition, structure,
Glass transition temperature, molecular weight, acid number etc. determine the physical property of photoresist, therefore to photic
The physical property of resist produces a very large impact.
Especially, in the alkali-developable binder polymer used in common negative type photoresist one
As mainly use pure acrylic resin, and the salt that this acrylic adhesives polymer is to composition etching solution
The acid resistance of the compositions such as acid, nitric acid is weak, causes many problems the most in the etch process.
To this end, as improving the acid proof method of photoresist, the present invention confirms in the polymer,
By excellent for chemical resistance epoxy-modified to acrylic acid in the case of, etching solution is had excellent acidproof
Property, and circuit adherence is the most excellent, easily dimmable coating mobility, and then complete the present invention.
Epoxy modified acrylic resin according to the present invention is: carry out being polymerized generating third at acrylic monomers
After olefin(e) acid polymer, the acrylate copolymer generated and epoxy resin carry out open loop in the presence of a catalyst
Polymerization, and then make the product that epoxy resin graft (grafting) obtains to acrylate copolymer.Now,
The polymerization of described acrylic monomers can be carried out 1 to 10 hour at 40 to 120 DEG C, described ring-opening polymerisation
Can carry out 1 to 8 hour at 60 to 100 DEG C, but be not limited to this.As long as can be by propylene
Acid resin is modified as method and condition known to the art of epoxy radicals, all can use.
That is, in the epoxy modified acrylic resin of the present invention, " epoxide modified " refers at acrylate copolymer
The meaning of upper grafting (grafting) epoxy resin, merely synthesizes with by acrylic monomers and epoxy resin
(synthesis) reaction difference.
Additionally, the weight ratio that content ratio is 70～95:5～30 of described acrylic monomers and epoxy resin,
In the case of above-mentioned content ratio, will not exhibit the characteristic of epoxy resin, or because of the ring of excess
Epoxy resins and make photoresist oxidant layer the softest, and then the problem that can occur can not be coated or be layered.
Additionally, the catalyst used in described ring-opening polymerisation, as long as can be used in epoxy addition reaction
Catalyst, can use without limitation.Specifically can enumerate zinc octoate, tin octoate, cobalt octoate etc..
Its addition can be 0.01 to 5 weight % in terms of reactant gross weight.
Described acrylic monomers can be enumerated such as styrene, methyl methacrylate, acrylic acid methyl ester., propylene
Acetoacetic ester, ethyl methacrylate, 2-ethylhexyl acrylate, isopropyl acrylate, methacrylic acid
Isopropyl ester, n-butyl acrylate, Isobutyl 2-propenoate, n-BMA, methacrylic acid are different
The most own ester of butyl ester, methacrylic acid, lauryl methacrylate, acrylic acid, methacrylic acid, 2-methyl
2-(Acryloyloxy)ethanol, 2-2-(Acryloyloxy)ethanol, Hydroxypropyl acrylate, hy-droxybutyl etc..Can also be by
They use respectively or are used in mixed way.
Additionally, as epoxy resin, can enumerate such as bisphenol-type epoxy resin, nobolak type epoxy tree
Fat, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, linear aliphatic epoxy resins,
Alicyclic epoxy resin and biphenyl type epoxy resin etc..From the point of view of in terms of operability and chemical resistance, preferably
Bisphenol-type epoxy resin therein.
Described bisphenol-type epoxy resin can pass through bisphenols and epoxychloropropane, Alpha-Methyl epoxychloropropane
Obtain Deng the reaction with halogenated epoxy.
Described bisphenols can enumerate as phenol or 2,6-dihalide phenol and formaldehyde, acetaldehyde, acetone, acetophenone,
The aldehydes such as Ketohexamethylene, benzophenone, or with the product of ketone and according to the peracidity of dihydroxy benzenes thioether
And the oxidation product produced, the esterification reaction product etc. of hydroquinone.In these bisphenol-type epoxy resins,
Especially it is widely used and preferably as bisphenol-A, bisphenol S, the Bisphenol F of bisphenols or use theirs
Hydrogenation products and the bisphenol-type epoxy resin that obtains.
Additionally, the preferred 180g/eq to 1500g/eq of the epoxide equivalent of described epoxy resin.Use epoxy is worked as
In the case of amount is less than the epoxy resin of 180g/eq, resin can be made tacky, use more than 1500g/eg's
In the case of epoxy resin, compatibility can reduce, and then can cause opaque, can produce and divide mutually time serious
From.
By the glass transition temperature of the acrylate copolymer of described polymerizable acrylic monomer be 40 to
150 DEG C, if the glass transition temperature of acrylate copolymer is less than 40 DEG C, the most after coating, with hot blast
The drying capacity being dried reduces, and can be tacky, and then is not suitable for using, and glass transition temperature is higher than 150 DEG C
Time, then film becomes fragile (brittle), frangible, therefore unsuitable preferred.
The acid number of the epoxy modified acrylic resin prepared according to the method described above is 100 to 250mg
KOH/g, in the case of the acid number of described epoxy modified acrylic resin is less than 100mg KOH/g, is entering
When row development and stripping technology, can be elongated with the response time of aqueous slkali, and then reduction production can be caused to receive
The problem of rate.In the case of 250mg KOH/g, storage container can be corroded when storage composition,
Or can aoxidize, reduction reaction etc., and, because of with contacting of base material (substrate) and produce in inside
Angry bubble, so can occur bad while, development and peeling rate are too fast, and then exist and be difficult in adapt to
Problem in operability.
The weight average molecular weight of described epoxy modified acrylic resin is 35,000 to 100,000g/mol, weight average
Molecular weight is less than 35, and in the case of 000g/mol, wandering character can become strong, and then is not suitable for use in film,
And there is the problem that acid resistance is substantially reduced.More than 100, in the case of 000g/mol, viscosity can rise,
And then make mobility be substantially reduced, there is the problem being difficult to prepare uniform coating.
In alkali-developable binder polymer according to the present invention, except epoxy-modified acrylic acid can be contained
Outside resin, it is also possible to contain acrylate copolymer further.Described acrylate copolymer will be for selecting
Free acrylic acid methyl ester., methyl methacrylate, ethyl acrylate, methyl methacrylate, acrylic acid
Butyl ester, butyl methacrylate, acrylic acid, methacrylic acid, 2-2-(Acryloyloxy)ethanol, 2-metering system
Acid hydroxyl ethyl ester, 2-Hydroxypropyl acrylate, 2-Hydroxypropyl methacrylate, acrylamide, Methacrylamide,
Two or more monomer in the linear acrylic macromolecule of styrene, α-methyl styrene synthesis is by altogether
The co-polypropylene acid macromolecule gathered and obtain.
Additionally, according to the alkali-developable binder polymer of the present invention in terms of photosensitive resin composition gross weight
Containing 20 to 80 weight %.The content of described alkali-developable binder polymer situation within the above range
Under, after the circuitry is formed, it is possible to obtain the effect making acid resistance and fine rule adhesion force strengthen.
Photoepolymerizationinitiater initiater (B)
Photoepolymerizationinitiater initiater contained in the photosensitive resin composition of the dry film photoresist of the present invention
It is the material of the chain reflex inducing photopolymerization monomer with UV and other radiation (radiation),
The solidification of dry film photoresist plays an important role.
Compound as described Photoepolymerizationinitiater initiater can be enumerated such as the anthracene such as 2-methylanthraquinone, 2-ethyl-anthraquinone
Naphthoquinone derivatives, benzoin methyl ether, diphenylmethanone, phenanthrenequione, 4,4 '-bis--(dimethylamino) benzophenone
Deng Benzoin derivative.
Further, it is also possible to will be selected from 2, double (the 2-chlorphenyl)-4,4 '-5 of 2-, 5 '-tetraphenyl bisglyoxaline, 1-hydroxyl ring
Hexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-ketone, 2-methyl isophthalic acid-[4-(methyl thio) benzene
Base]-2-morpholino propane-1-ketone, 2-benzyl-2-dimethylamino-1-[4-morphlinophenyl] butane-1-ketone, 2-hydroxyl
Base-2-methyl isophthalic acid-phenyl-propane-1-ketone, 2,4,6-trimethyl benzoyl diphenyl base phosphine oxide, 1-[4-(2-hydroxyl
Ylmethoxy) phenyl]-2-hydroxy-2-methyl propane-1-ketone, 2,4-diethyl thioxanthone, CTX, 2,4-
Dimethyl thioxanthone, 3,3-dimethyl-4-methoxyl group diphenylmethanone, diphenylmethanone, 1-chloro-4-propoxyl group
Thiaxanthone, 1-(4-isopropyl phenyl) 2-hydroxy-2-methyl propane-1-ketone, 1-(4-dodecylphenyl)-2-hydroxyl
Base-2-methylpropane-1-ketone, 4-benzoyl-4 '-methyl dimethoxy base thioether, 4-dimethylaminobenzoic acid,
4-dimethylaminobenzoic acid methyl ester, EDMAB, 4-dimethylaminobenzoic acid fourth
Ester, 4-dimethylaminobenzoic acid 2-Octyl Nitrite, 4-dimethylaminobenzoic acid 2-isopentyl ester, 2,2-bis-
Acetophenone, benzyl ketone dimethylacetal, benzyl ketone 'beta '-methoxy diethyl ketal, 1-phenyl-1,2-
Propyl group dioxime-o, o '-(2-carbonyl) ethyoxyl ether, methyl o-benzoylbenzoate, double [4-dimethylamino benzene
Base] ketone, 4,4 '-bis-(diethylamino) benzophenones, 4,4 '-dichloro-benzenes ketone, benzil, Benzoinum, first
Epoxide Benzoinum, ethoxy ethyl perfume, isopropoxy Benzoinum, n-butoxy Benzoinum, isobutoxy
Benzoinum, three grades of butoxy Benzoinumes, to dimethylamino benzoylformaldoxime, to three grades of butyl trichloroacetophenones,
To three grades of butyl dichloroacetophenones, thiaxanthone, 2-methyl thiaxanthone, ITX, dibenzo ring
Heptane, α, the compound in α,α-dichloro-4-phenoxy acetophenone, 4-dimethylaminobenzoic acid pentyl ester is as light
Polymerization initiator uses, but is not limited to this.
The content of described Photoepolymerizationinitiater initiater in terms of photosensitive resin composition gross weight containing 2 to 10 weight %.
The content of described Photoepolymerizationinitiater initiater within the above range time, it is possible to obtain sufficient sensitivity, exposure
During operation, it is possible to reduce the physical property deviation caused because of exposer or other external condition.
Photopolymerizable compound (C)
Olefinically unsaturated compounds has polyfunctional monomer and monofunctional monomer, as polyfunctional monomer, enumerates
There are ethylene glycol dimethacrylate (ethylene glycol dimethacrylate), dimethacrylate two sweet
Alcohol ester (diethylene glycol dimethacrylate), tetraethylene glycol dimethacrylate (tetraethylene
Glycol dimethacrylate), dimethacrylate (propylene glycol
Dimethacrylate), polypropylene glycol dimethacrylate (polypropylene glycol
Dimethacrylate), butanediol dimethylacrylate (butylene glycol dimethacrylate), diformazan
Base diacrylate peopentyl ester (neopentyl glycol dimethacrylate), 1,6-HD dimethacrylate
Ester (1,6-hexane glycol dimethacrylate), trimethylol-propane trimethacrylate
(trimethyolpropane trimethacrylate), glycerol dimethacrylate (glycerin
Dimethacrylate), dimethyl pentaerythritol acrylate (pentaerythritol dimethacrylate), season
Penta tetrol trimethyl acrylic ester (pentaerythritol trimethacrylate), dipentaerythritol pentamethyl propylene
Double (the 4-methacryloxy diethoxybenzene of acid esters (dipentaerythritol pentamethacrylate), 2,2-
Base) propane (2,2-bis (4-methacryloxydiethoxyphenyl) propane), 2-hydroxy-3-methyl acryloyl
Epoxide propyl methacrylate (2-hydroxy-3-methacryloyloxypropyl methacrylate), second two
Alcohol diglycidyl ether 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..
With the monofunctional monomer that polyfunctional monomer could be used with appropriate amount.As monofunctional monomer,
Such as there are HEMA (2-hydroxyethyl methacrylate), methacrylic acid 2-hydroxypropyl
Ester (2-hydroxypropyl methacrylate), methacrylic acid 2-hydroxy butyl ester (2-hydroxybutyl
Methacrylate), 2-phenoxy group-2-HPMA (2-phenoxy-2-hydroxypropyl
Methacrylate), 2-methacryloxy-2-phthalic acid hydroxypropyl acrylate
(2-methacryloyloxy-2-hydroxypropyl phthalate), 3-chloro-2-HPMA
(3-chloro-2-hydroxypropyl methacrylate), glycerol monomethacrylate (glycerin
Monomethacrylate), 2-first acryloyl-oxyethyl acid phosphoric acid ester (2-methacryloyloxyethyl acid
Phosphate), phthalic acid (phthalic acid) methacrylate of derivant, N-hydroxymethyl, methyl
Acrylamide (N-methylol methacrylamide), 2,2 '-bis--[4-(methacryloxy-polyethoxy)
Phenyl] propane, Polyethylene Glycol polypropylene glycol dimethacrylate etc..
Described photopolymerizable compound can contain 10 to 70 weight % in photosensitive resin composition.Described
The content of photopolymerizable compound within the above range time, there is strengthening lightsensitivity and adhesion force and resolution
The effect of the circuit physical property such as rate.
Solvent and other additive (D)
The solvent of the photosensitive resin composition of the present invention, generally can butanone (MEK), methanol, four
Selecting in hydrogen furan (THF), toluene, acetone to use, to described solvent, there is no particular limitation, content
Still can containing according to Photoepolymerizationinitiater initiater, alkali-developable binder polymer and photopolymerizable compound
Amount is adjusted.
Additionally, the photosensitive resin composition of the present invention can also comprise other additives as required, as
Other additives, it is possible to use as plasticizer phthalic acid ester form dibutyl phthalate,
Dibutyl phthalate (DHP), dioctyl phthalate, diallyl phthalate；Glycol ester shape
The triethylene glycol diacetate of state, TEG diacetate；Acid amide form para toluene sulfonamide,
Benzsulfamide, nbutylbenzenesulfonamide；Triphenyl phosphate etc..
In order to improve the treatability of the photosensitive resin composition of the present invention, it is also possible to add leuco dye or
Color substance.Described leuco dye can enumerate three (4-dimethylamino-2-aminomethyl phenyl) methane, three (4-diformazans
Base amino-2 aminomethyl phenyl) methane, fluoran dyestuff etc..Wherein, in the situation using LCV
Under, because contrast is good and preferred.In the case of containing leuco dye, its content is preferably in photosensitive tree
Containing 0.1 to 10 weight % in oil/fat composition.From the viewpoint of the expression of contrast, preferably 0.1 weight %
Above, from the viewpoint of maintaining storage stability, below preferably 10 weight %.
As coloring material, toluenesulfonic acid monohydrate, basic fuchsin, phthalocyanine green, auramine can be enumerated
Alkali, para magenta, crystal violet, methyl orange, Nile blue 2B, Victoria blue, peacock green, diamond green,
Alkali blue 20 etc..In the case of above-mentioned coloring material, its content is preferably in photosensitive resin composition
Containing 0.001 to 2 weight %.There is under content more than 0.001 weight % the effect improving treatability,
There is under content below 2 weight % the effect maintaining storage stability.
Furthermore, it is possible to contain the thermal polymerization preventing agent as other additives, dyestuff, colour-changing agent further
(discoloring agent), adhesion force accelerator etc..
In the present invention, the photosensitive resin composition of composition as described above can be prepared as dry film photoresist
The photosensitive resin composition of agent, on the common base films such as polyethylene terephthalate, uses
Common coating process, after being coated with photosensitive resin layer with the thickness of 5 to 200 μm so that it is be dried, in institute
Stating the above of dry photosensitive resin layer can utilize the common protective films such as polyethylene to be laminated, and enters
And prepare dry film.Thus obtained dry film is exposed, develops, then uses the side evaluating each physical property
Method is carried out.
Below, the preferred embodiments of the present invention and comparative example are illustrated.But, following embodiment is only
Being a preferred embodiment of the present invention, the present invention is not limited to following embodiment.
[preparation example 1 to 3]
Four mouthfuls of round bottom beakers are installed thermometer, mechanical stirrer (mechanical stirrer) and backflow
After device, nitrogen is used to purify inside beaker.Beaker after using nitrogen to purify adds 90g first and second
Ketone (Methyl Ethyl Ketone, MEK) and 10g propylene glycol monomethyl ether acetate (Propylene Glycol
Monomehtyl Ether Acetate, PGMEA) after, add 1.5g azodiisobutyronitrile
(azobisisobutyronitrile, AIBN) so that it is be completely dissolved.The acrylic acid described in table 1 is added at this
Monomer, is polymerized 6 hours at 80 DEG C, and then obtains acrylate copolymer.Acrylic acid in above-mentioned generation
(epoxide equivalent 450g/eq, YD-011, state all changes to add 15g bisphenol A type epoxy resin in polymer
Learn) and 0.5g zinc octoate (Aldrich), ring-opening reaction 6 hours at 80 DEG C, and then prepared alkali-developable
Binder polymer.
[preparation example 4 and 5]
After four mouthfuls of round bottom beakers install mechanical stirrer, thermometer and reflux, use nitrogen
Inside purification beaker.0.8g AIBN is added so that it is the most molten in 90g MEK and 10g PGMEA
Solve.Then the 100g monomer described in table 1 is joined in beaker, be polymerized 6 hours at 80 DEG C.
The physical property utilizing the following method binder polymer to preparing in described preparation example is measured, its
Result is shown in Table 1.
(1) acid value measuring
Sampling 1g binder polymer, be dissolved in 50ml mixed solvent (methanol (MeOH) 20%,
Acetone (Acetone) 80%) in, add 2 1%-phenolphthalein reagents, then carry out with 0.1N-KOH
Titration, and then measure acid number.
(2) molecular weight determination
Measure use polyphenyl according to gel permeation chromatography (GPC) (water (Waters): Waters707)
The weight average molecular weight (Mw) of ethylene conversion and number-average molecular weight (Mn).By obtained in above-mentioned preparation example
Binder polymer be dissolved in oxolane, make concentration become 4000ppm, then by 100 μ l inject
In GPC.The flowing of GPC uses oxolane mutually, flows into the flow velocity of 1.0ml/ minute, and analysis is
Carry out at 35 DEG C.Using Waters HR-05,1,2,4E these four be connected in series as chromatography tubing string.
RI and PAD Detector detector is used to be measured at 35 DEG C.Now, the weight average of mensuration is divided
Son amount is calculated PDI (polydispersity index) divided by number-average molecular weight.
(3) glass transition temperature measures
Differential Scanning Calorimeter analyser (Differential Scanning Calorimeter,
DSC) comparative control (reference) adhesive composition in (Perkin-Elmer company, DSC-7).Will
Temperature be set at 20 DEG C maintenance 15 minutes after, with the programming rate of 1 DEG C/min be warming up to 200 DEG C laggard
Row measures.
[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 number (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]
According to the composition shown in table 2 below, the photosensitive resin composition of dry film photoresist is carried out
Preparation and coating, and then be evaluated.First, Photoepolymerizationinitiater initiater class is dissolved in first and second as solvent
In ketone (MEK), then, the alkali-developable binding agent polymerization of photopolymerizable compound and preparation example is added
Thing, utilizes mechanical agitator to mix about about 1 hour, and then obtains photosensitive resin composition.Utilize and be coated with
The photosensitive resin composition of above-mentioned acquisition is coated in the PET film of 20 μm by cloth rod (bar).Utilize
The photosensitive resin composition layer of coating is dried by hot-blast oven, and baking temperature now is 80 DEG C, dry
The dry time is 5 minutes, and the thickness of dried photosensitive resin composition layer is 20 μm.Utilize protective film
(polyethylene) will complete the film laminating that is dried to photosensitive resin layer.
[table 2]
To using the photosensitive resin composition and then prepared dry film photoresist prepared according to above-mentioned composition
Implement following technique.
<lamination>
With basal plate preheating roll temperature be 120 DEG C, laminating roll temperature be 115 DEG C, roller pressure is as 4.0kgf/cm2、
Roller speed is that dry film photoresist is laminated by the condition of 2.5min/m.In order to confirm circuit characteristic,
Use the ito thin film of NITTO DENKO company as material, in order to implement ageing of metal (metal
Aging), at 120 DEG C implement 30 minutes aging.
<development>
On ito thin film, use the light shield for evaluating circuit, and utilize Perkin-ElmerTM
OB7120 (parallel exposing machine), in 41 grades of stages, the light exposure with 16 grades is photic to the dry film of lamination
After resist irradiation ultraviolet radiation respectively, place 20 minutes, then by the 1.0wt%Na of 30 DEG C2CO3Water
Solution is with 1.5kgf/cm2Pressure spray and develop.Measure unexposed dry film light on ito thin film
Cause the time (minimum developing time) that the developed liquid of resist is removed completely, and its result is recorded in table 3
In.
<circuit characteristic evaluation>
Circuit characteristic evaluation be develop with 2 times of minimum developing times after, utilize ultramicroscope to carry out
Evaluate.Now, fine rule adhesion force after development, has the minimum feature of independent resist with retention,
Utilize ZEISS AXIOPHOT Microscope to be measured, resolution be by circuit line and circuit line it
Between space be set to the value that the ratio of 1:1 is measured, it utilizes ZEISS AXIOPHOT Microscope
It is measured.Its result is recorded in table 3.
<acid resistance evaluation>
The ito thin film completing development is put in the cup equipped with ITO etching solution, after placing certain time,
Confirm remaining minimum pattern (pattern), and be recorded in table 4.
[table 3]
As shown in table 3, it is possible to confirm that embodiment 1 to 3, compared with comparative example 1 and 2, remains similar
The fine rule adhesion force of level and resolution, and, the minimum developing time of comparative example 1 and 2 was less than 10 seconds
And too fast, therefore, it is difficult to it is suitable for operability.
[table 4]
As shown in table 4, it is possible to confirm that embodiment 1 to 3, compared with comparative example 1 and 2, has excellence
Acid resistance.
It is all that those skilled in the art are caned and easily implemented to the simple deformation of the present invention and change,
The most above-mentioned deformation or change are all contained in the scope of the present invention.
[industrial applicibility]
The photosensitive resin composition of the dry film photoresist according to the present invention has the fine rule adherence of excellence
While property and resolution, the most excellent to the acid resistance of etching solution, can apply to printed circuit board (PCB) (PCB)
Preparation and the process industry such as the contact panel that uses as sensor and electrode using ITO in, it is possible to increase
Quality and productivity ratio.
Claims (6)
1. a photosensitive resin composition for dry film photoresist, is characterized by,
The photosensitive resin composition of this dry film photoresist contains: alkali-developable binder polymer
(A), Photoepolymerizationinitiater initiater (B) and photopolymerizable compound (C),
Described alkali-developable binder polymer (A) contains epoxy modified acrylic resin.
The photosensitive resin composition of dry film photoresist the most according to claim 1, its feature
For,
The acid number of described epoxy modified acrylic resin is 100 to 250mg KOH/g, and weight average molecular weight is
35,000 to 100,000g/mol.
The photosensitive resin composition of dry film photoresist the most according to claim 1, its feature
For,
Described epoxy modified acrylic resin is, makes acrylic monomers carry out being polymerized and generating acroleic acid polymerization
After thing, the acrylate copolymer generated and epoxy resin are carried out in the presence of a catalyst ring-opening polymerisation and
The product obtained.
The photosensitive resin composition of dry film photoresist the most according to claim 3, its feature
For,
The epoxide equivalent of described epoxy resin is 180g/eq to 1500g/eq.
The photosensitive resin composition of dry film photoresist the most according to claim 3, its feature
For,
Described epoxy resin is selected from bisphenol-type epoxy resin, phenolic resin varnish type epoxy resin, ethylene oxidic ester
Type epoxy resin, glycidyl amine type epoxy resin, linear aliphatic epoxy resins, ester ring type asphalt mixtures modified by epoxy resin
More than one in fat and biphenyl type epoxy resin.
The photosensitive resin composition of dry film photoresist the most according to claim 1, its feature
For,
Described photosensitive resin composition contain 20 to 80 weight % alkali-developable binder polymer (A),
The Photoepolymerizationinitiater initiater (B) of 2 to 10 weight % and the photopolymerizable compound (C) of 10 to 70 weight %.
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| KR20130162183 | 2013-12-24 | ||
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| 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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| CN111123647A (en) * | 2020-01-14 | 2020-05-08 | 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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| JP6892376B2 (en) * | 2017-02-14 | 2021-06-23 | 信越化学工業株式会社 | Bioelectrode composition, bioelectrode, method for producing bioelectrode, and polymer compound |
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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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| JP4093335B2 (en) * | 2000-01-26 | 2008-06-04 | 日本化薬株式会社 | Photocationic curable dry film resist and cured product thereof |
| 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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| 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 |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111123647A (en) * | 2020-01-14 | 2020-05-08 | 广东省石油与精细化工研究院 | Dry film photoresist and application thereof |
| 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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| KR101692003B1 (en) | 2017-01-03 |
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| CN105849640B (en) | 2019-11-26 |
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