CN108490737A - A kind of photosensitive polymer combination and application thereof - Google Patents
A kind of photosensitive polymer combination and application thereof Download PDFInfo
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- CN108490737A CN108490737A CN201810209258.0A CN201810209258A CN108490737A CN 108490737 A CN108490737 A CN 108490737A CN 201810209258 A CN201810209258 A CN 201810209258A CN 108490737 A CN108490737 A CN 108490737A
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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
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
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- Chemical Kinetics & Catalysis (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Materials For Photolithography (AREA)
- Manufacturing Of Printed Circuit Boards (AREA)
Abstract
The invention discloses a kind of photosensitive polymer combinations and application thereof, the resin combination includes the binder polymer of 30 70 parts by weight, the photo polymerization monomer of 10 50 parts by weight, 0.5 10.0 parts by weight photoinitiators and 0.1 10.0 parts by weight additives, ethylenical unsaturated double bonds mole is 0.5 2.0m mol/g resin combinations in photo polymerization monomer, and additive contains ethylene oxide propylene oxide block copolymer；Ethylenical unsaturated double bonds mole in dosage and photo polymerization monomer that the present invention passes through regulation and control ethylene oxide propylene oxide block copolymer, when so that obtained resin combination being used as dry film photoresist, with moving back film easy fracture, move back that film chip size is moderate, characteristics such as fast of moving back film speed, circuit resolution ratio, adhesive force and flexibility are excellent simultaneously, it can thus improve and move back membrane efficiency, and then improve production efficiency and product yield.
Description
Technical field
The invention belongs to printed wiring board field, it is related to a kind of photosensitive polymer combination and application thereof.
Technical background
Printed wiring board is a kind of insulation board with printed circuit, has rigidity, flexibility and hard and soft knot according to hardness division
Close three kinds.Wherein, flexible circuit board is also known as flexible circuit board, flex circuit application, abbreviation soft board or FPC, high with Distribution density,
It is light-weight, thickness is thin, wiring space less-restrictive, the advantages that flexibility ratio is high, comply fully with the light and short development of electronic product
Trend is the effective workaround for meeting miniaturization of electronic products and movement requirement.FPC can with free bend, winding, folding,
And the dynamic bending that can bear millions of times can require arbitrary arrangement, and in three-dimensional space without damaging conducting wire according to space layout
Between arbitrarily move and flexible, the integrated effect connected to reach components and parts assembling with conducting wire.FPC can be substantially reduced electronics
The volume and weight of product is applicable in the needs that electronic product develops to high density, miniaturization, highly reliable direction.Therefore, it answers extensively
For the fields such as PC and peripheral product, automotive electronics, medical instrument, communication product and consumer electrical product.
In recent years, high density FPC is quickly grown, and line density is continuously increased diversification with interlayer structure, multiple stratification, makes
Line manufacturing process is obtained in face of more challenges.Wherein, it is one of critical process during FPC makes to move back film, and plate face moves back the clean journey of film
Degree directly affects the production of subsequent handling, and moving back film speed influences production efficiency.During produced on-site, since FPC thickness is thin, easy
The reason of flexural deformation, in order to prevent its fold in the machine in addition snap-gauge and cause to scrap, it will usually there are two to arrange
It applies, first, adding hard directing plate before FPC, is connected between the two with adhesive tape；Film spray pressure is moved back second is that reducing, moves back membrane pressure
Power is controlled in 0.3-2.0Kg/cm2In range.
But above-mentioned two measures can bring adverse effect.First, adhesive tape junction, photosensitive polymer combination are not easy
Fracture, it is clean to lead to move back film, influences subsequent handling production.At the same time, it reduces and moves back film pressure, can extend and move back the film time,
Reduce production efficiency.It is provided in patent document CN1828111B a kind of for implementing the anti-of two or more different electroless plating
Plating photosensitive polymer combination is resisted by regulating and controlling the reactive group total moles of ethylene formula unsaturated group in resin combination
It plating property and moves back film stripping and has excellent performance, Unfortunately, film problem is not moved back to FPC and makees further research.Patent document
CN102144189B provides a kind of photosensitive polymer combination, by polyoxyethylene (three (the 1- benzene for adding ethylene oxide modification
Base ethyl)) phenyl ether, resolution ratio, adhesive force, cap bore are had excellent performance, while stripping performance is excellent, but are not moved back to FPC
Film problem is for further study.
Invention content
In view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to provide a kind of photosensitive polymer combination and application thereof.
The purpose of the present invention is what is be achieved through the following technical solutions：A kind of photosensitive polymer combination, the described resin
Composition includes：The binder polymer of 30-70 parts by weight, the photo polymerization monomer of 10-50 parts by weight, 0.5-10.0 parts by weight
The additive of photoinitiator and 0.1-10.0 parts by weight.Wherein, ethylenical unsaturated double bonds mole is in the photo polymerization monomer
0.5-2.0mmol/g resin combinations, in additive shown in the general formula (I) containing 0.1-10.0 parts by weight or general formula (II)
Ethylene oxide-propylene oxide block copolymer.
In formula (I), x1, y1 and z1 are separate positive integer, and 7≤x1+y1+z1≤227.
In formula (II), x2, y2 and z2 are separate positive integer, and 7≤x2+y2+z2≤227.
Further, ring shown in 1.0-7.0 parts by weight general formula (I) or general formula (II) is preferably comprised in the additive
Oxidative ethane-propylene oxide block copolymer；Ethylene oxide-propylene oxide block copolymer preferably 17 shown in the general formula (I)
≤x1+y1+z1≤200；Ethylene oxide-propylene oxide block copolymer preferably 17≤x2+y2+z2 shown in the general formula (II)
≤200。
Further, the photo polymerization monomer is the undersaturated monomer of vinyl.
Further, the photo polymerization monomer is by (methyl) lauryl acrylate, (methyl) octadecyl acrylate, nonyl
It is base phenol acrylate, ethoxyquin (third oxidation) nonyl phenol acrylate, isobornyl thiocyanoacetate, acrylic acid tetrahydrofuran methyl esters, double
Phenol A bis- (methyl) acrylate, ethoxyquin (the third oxidation) bisphenol-A two (methyl) acrylate, two (first of polyethylene glycol (propylene glycol)
Base) acrylate, ethoxyquin (third oxidation) neopentylglycol diacrylate, trimethylolpropane tris (methyl) acrylate, second
Oxidation (the third oxidation) trimethylolpropane tris (methyl) acrylate, pentaerythritol triacrylate, pentaerythrite tetrapropylene acid
One or more compositions in ester, Dipentaerythritol Pentaacrylate, dipentaerythritol hexaacrylate.
Further, the photoinitiator is selected from 2,4,5- triarylimidazoles dimers and its derivative, thioxanthones, benzene are even
Relation by marriage phenyl ether, benzophenone, benzoin methyl ether, N, N'- tetramethyl -4,4'- diaminobenzophenones, N, tetraethyl -4 N'-,
4'- diaminobenzophenones, 4- methoxyl group -4'- dimethylamino benzophenones, 2- benzyl -2- dimethylamino -1- (4-
Quinoline base phenyl)-butanone, 2- ethyl hydrazine, phenanthrenequione, 2- tertiary butyls anthraquinone, prestox anthraquinone, 1,2 benzae thracene quinone, 2,3- benzos
Anthraquinone, 2,3- diphenyl anthraquinone, 1- chloroanthraquinones, 2-methylanthraquinone, 1,4- naphthoquinones, 9,10- phenanthrenequione, 2,3- dimethyl anthraquinone, peace
Benzil derivatives, 9- phenylacridines, 1 such as the fragrant methyl ether of breath, benzoin ethyl ether, styrax phenyl ether, benzil dimethyl ketal,
Acridine derivatives, N-phenylglycine, coumarin series compounds, the oxazole based compounds such as 7- bis- (9,9'- acridinyls) heptane；Institute
It includes 2- (Chloro-O-Phenyl) -4,5- diphenyl-imidazoles dimer, 2- (neighbours to state 2,4,5- triarylimidazoles dimer and its derivative
Chlorphenyl) -4,5- two (methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5- diphenyl-imidazoles dimer, 2- be (adjacent
Methoxyphenyl) -4,5- diphenyl-imidazoles dimer, 2- (p-methoxyphenyl) -4,5- diphenyl-imidazole dimers.
Further, the photoinitiator preferably 2,2 ', 4- tri- (2- chlorphenyls) -5- (3,4- Dimethoxyphenyl) -4 ',
5 '-diphenyl -1,1 '-diimidazole.
Further, described adhesive polymer is copolymerized to obtain by unsaturated carboxylic acid and vinyl compound, polymeric acid
Value is in 100-300mg KOH/g resins, weight average molecular weight 30,000-150,000.
Further, the preferred 100-300mg KOH/g resins of the polymer acid number, weight average molecular weight preferably 30,000-
150,000；The more preferable 120-200mg KOH/g resins of polymer acid number, weight average molecular weight more preferable 40,000-100,
000。
The present invention also provides the purposes that a kind of above-mentioned photosensitive polymer combination is used as dry film photoresist, the purposes is specific
For the dry film photoresist can carry out pad pasting, 80-110 DEG C of pad pasting temperature, pressure 4.0-7.0Kg/cm with wet processing2, speed
1.0-3.0m/min。
The present invention also provides the purposes that a kind of above-mentioned photosensitive polymer combination is used as dry film photoresist, the purposes is specific
For the dry film photoresist can carry out moving back film under the conditions of Low-pressure spray, move back film pressure 0.3-2.0Kg/cm2。
The invention has the advantages that the present invention by regulate and control ethylene oxide-propylene oxide block copolymer dosage with
And ethylenical unsaturated double bonds mole in photo polymerization monomer, solve technical problem of the existing technology.Obtained by the present invention
Resin combination when being used as dry film photoresist, have and move back film easy fracture, move back that film chip size is moderate, the spies such as fast that move back film speed
Property, while circuit resolution ratio, adhesive force and flexibility are excellent, it is thus possible in the flexible print circuit using wet film coating process
When plate manufactures, membrane efficiency is moved back in raising, and then improves production efficiency and product yield.
Specific implementation mode
The present invention provides a kind of photosensitive polymer combination for dry film photoresist, and the described resin combination includes：
The binder polymer of 30-70 parts by weight, the photo polymerization monomer of 10-50 parts by weight, 0.5-10.0 parts by weight photoinitiator, 0.1-
10.0 parts by weight additive.
As the binder polymer of the present invention, preferably carboxylic vinyl group resin, by unsaturated carboxylic acid and ethylene
Based compound is copolymerized to obtain.The unsaturated carboxylic acid can enumerate (methyl) acrylic acid, butenoic acid, methacrylate, maleic acid,
Maleic anhydride, itaconic acid, crotonic acid etc..The vinyl compound can enumerate (methyl) methyl acrylate, (methyl) third
Olefin(e) acid ethyl ester, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) amyl acrylate, (methyl) Hexyl 2-propenoate,
(methyl) lauryl acrylate, (methyl) octadecyl acrylate, (methyl) acrylate, (methyl) hydroxy-ethyl acrylate,
(methyl) benzyl acrylate, styrene, α-methylstyrene, hydroxy styrenes, (methyl) acrylamide, N- methylols-propylene
Amide, N- butoxymethyls-acrylamide, Phenoxyethyl (methyl) acrylate, (alkoxylate) nonyl phenol (methyl)
Acrylate, N, N- dimethyl (methyl) ethyl acrylate, N, N- diethyl (methyl) ethyl acrylate, N, N- dimethyl (first
Base) propyl acrylate, N, N- diethyl (methyl) propyl acrylate etc..Carboxylic vinyl group resin can be by above-mentioned one kind
Or a variety of unsaturated carboxylic acids and one or more vinyl compounds are copolymerized and obtain.The available well known method of preparation method, such as
Polymerisation in solution, suspension polymerisation etc..
In the present invention, (methyl) acrylate indicates acrylate and methacrylate, ethoxyquin (the third oxidation) third
Olefin(e) acid ester indicates that ethoxyquin acrylate and ethoxyquin third aoxidize the acrylate of hydridization.
The acid value of above-mentioned binder polymer ingredient, from the aspect of developing powder and developer resistance two, preferably 100-
300mgKOH/g resins, more preferable 120-200mg KOH/g resins.The weight average molecular weight of above-mentioned binder polymer (uses gel
Permeation chromatography (GPC) measures, and is converted using standard polystyrene calibration curve) preferably 30,000-150,000, more preferable 40,
000-100,000。
As the photo polymerization monomer of the present invention, the i.e. undersaturated monomer of vinyl, (methyl) acrylic acid moon can be enumerated
Osmanthus ester, (methyl) octadecyl acrylate, nonyl phenol acrylate, ethoxyquin (the third oxidation) nonyl phenol acrylate,
Isobornyl thiocyanoacetate, acrylic acid tetrahydrofuran methyl esters, bisphenol-A two (methyl) acrylate, ethoxyquin (the third oxidation) bisphenol-A two (methyl)
Acrylate, polyethylene glycol (propylene glycol) two (methyl) acrylate, ethoxyquin (the third oxidation) neopentylglycol diacrylate, three
Hydroxymethyl-propane three (methyl) acrylate, ethoxyquin (the third oxidation) trimethylolpropane tris (methyl) acrylate, Ji Wusi
Alcohol triacrylate, pentaerythritol tetraacrylate, Dipentaerythritol Pentaacrylate, dipentaerythritol hexaacrylate etc..
In the present invention, ethylenical unsaturated double bonds mole is 0.5-2.0m mol/g resin combinations in photo polymerization monomer
Object.If double bond mole is less than 0.5m mol/g resin combinations, resolution ratio and the attachment of dry film photoresist can be substantially reduced
Power；If double bond mole is higher than 2.0m mol/g resin combinations, photosensitive polymer combination crosslink density is excessively high, influences to move back
Film properties.
As the photoinitiator of the present invention, contains 2,4,5- triarylimidazoles dimers and its derivative, can enumerate
2- (Chloro-O-Phenyl) -4,5- diphenyl-imidazoles dimer, two (methoxyphenyl) imidazole dimers of 2- (Chloro-O-Phenyl) -4,5-,
2- (o-fluorophenyl) -4,5- diphenyl-imidazoles dimer, 2- (o-methoxyphenyl) -4,5- diphenyl-imidazoles dimer, 2- are (right
Methoxyphenyl) -4,5- diphenyl-imidazole dimers etc., preferably 2,2 ', 4- tri- (2- chlorphenyls) -5- (3,4- dimethoxy benzenes
Base) -4 ', 5 '-diphenyl -1,1 '-diimidazole.Further, it is also possible to thioxanthones, benzoin phenyl ether, benzophenone, benzoin
Methyl ether, N, N'- tetramethyl -4,4'- diaminobenzophenones, N, N'- tetraethyl -4,4'- diaminobenzophenones, 4- methoxies
Base -4'- dimethylamino benzophenones, 2- benzyl -2- dimethylaminos -1- (4- morpholino phenyls)-butanone, 2- ethyl anthracenes
Quinone, phenanthrenequione, 2- tertiary butyls anthraquinone, prestox anthraquinone, 1,2 benzae thracene quinone, 2,3- benzos anthraquinone, 2,3- diphenyl anthraquinone, 1- chlorine
Anthraquinone, 1,4- naphthoquinones, 9,10- phenanthrenequione, 2,3- dimethyl anthraquinone, benzoin methyl ether, benzoin ethyl ether, is rested in peace at 2-methylanthraquinone
The benzil derivatives such as fragrant phenyl ether, benzil dimethyl ketal, 9- phenylacridines, 1,7- bis- (9,9'- acridinyls) heptane etc.
Acridine derivatives, N-phenylglycine, coumarin series compounds, oxazole based compound etc..
As the additive of the present invention, contain epoxy ethane-epoxy propane block shown in general formula (I) or general formula (II)
Copolymer.
In formula (I), x1, y1 and z1 are separate positive integer, 7≤x1+y1+z1≤227.
In formula (II), x2, y2 and z2 are separate positive integer, 7≤x2+y2+z2≤227.
The parts by weight of above-mentioned ethylene oxide-propylene oxide block copolymer, from the aspect of moving back film properties and adhesive force two,
It is preferred that 0.1-10.0, more preferable 1.0-7.0.If parts by weight are less than 0.1, the performance for moving back film can be significantly affected；If parts by weight
Higher than 10.0, the adhesive force of photosensitive polymer combination can be substantially reduced.
As the ethylene oxide-propylene oxide block copolymer of the present invention, the poly- second of polypropylene glycol-block- can be enumerated
Glycol-block- polypropylene glycols, average molecular weight are respectively 2000,2700,3300；Polyethylene glycol-block- polypropylene glycols-
Block- polyethylene glycol, average molecular weight are respectively 1100,1900,2000,2800,2900,4400,5800,8400, and reagent comes
From Aldrich.
In the present invention, can be as needed, the light quality such as dyestuff of the addition containing malachite green etc, colorless crystal violet
Agent, quality heat stabilizer, plasticizer, pigment, filler, antifoaming agent, fire retardant, stabilizer, levelling agent, stripping accelerating agent, antioxygen
Agent, fragrance, preparation, thermal cross-linking agent etc..
The resin combination of the present invention, can be as needed, is dissolved in methanol, ethyl alcohol, isopropanol, acetone, butanone, first
The mixed solvent of benzene, N,N-dimethylformamide, propylene glycol monomethyl ether, propylene glycol methyl ether acetate equal solvent or these solvents
In.
With reference to embodiment, the invention will be further described, but protection scope of the present invention is not only limited to implement
Example.
(embodiment 1-6, comparative example 1-6)
Each component is mixed in proportion according to the formula of following table 1 and table 2, the acetone of 60 parts by weight is added, then fully
Stirring is made into the resin composition solution that solid content is 40% to being completely dissolved.Using coating machine it was evenly coated on as
Surface PET film (thickness 15um) of support membrane, is placed in 85 DEG C of baking ovens and dries 10min, forms the dry film photoresist that thickness is 20um
Green is presented in layer under yellow fluorescent lamp.Then, the polyethylene film in the fitting of its surface as protective layer, thickness 20um, in this way
The photosensitive dry film of 3-tier architecture is just obtained.
It should be noted that in Tables 1 and 2 binder polymer A be oneself prepare, using solution polymerization process, mainly at
Be divided into methacrylic acid/acrylic acid/methyl methacrylate/n-BMA/lauryl acrylate/styrene=
18/5/45/15/9/8 (Mw=72,000).
Photo polymerization monomer：
B-1：(8) ethoxylated nonylphenol acrylate, molecular weight 626 (Sartomer)
B-2：(9) ethoxyquin dimethylacrylate, molecular weight 598 (U.S. source)
B-3：(3) (17) third cacodyl oxide base acrylate of ethoxyquin, molecular weight 1330 (U.S. source)
B-4：(6) ethoxyquin trimethylolpropane trimethacrylate, molecular weight 560 (Sartomer)
B-5：(3) ethoxyquin trimethylolpropane trimethacrylate, molecular weight 428 (Sartomer)
Photoinitiator：
C-1：2,2 ', 4- tri- (2- chlorphenyls) -5- (3,4- Dimethoxyphenyls) -4 ', 5 '-diphenyl -1,1 '-diimidazole
(Changzhou electronic strong new material)
C-2：N-phenylglycine (West Asia chemistry)
Additive:
D-1：Polypropylene glycol-block- polyethylene glycol-block- polypropylene glycols, average molecular weight are 2700 (Aldrich)
D-2：Polyethylene glycol-block- polypropylene glycol-block- polyethylene glycol, average molecular weight are 2000 (Aldrich)
D-3：Polyethylene glycol-block- polypropylene glycol-block- polyethylene glycol, average molecular weight are 4400 (Aldrich)
D-4：Magnificent green pigment (Shanghai lark waffle Technology Co., Ltd.)
D-5：Leuco crystal violet (Shanghai lark waffle Technology Co., Ltd.)
D-6：Trisbromomethyl phenyl sulfone (the uncommon love chemical industry of Shanghai ladder)
D-7：N, N- diethyl hydroxylamine (Shanghai lark waffle Technology Co., Ltd.)
Table 1
Table 2
Hereinafter, illustrating that the sample production method of embodiment and comparative example (including pad pasting, exposure, development, acid etching, is moved back
Film), sample evaluation method and evaluation result.
【Wet film coating】
Double-faced flexible copper-clad plate (FCCL) a, is cut into the rectangle of 25*20cm, using laser drilling machine in flexible base board
The upper aperture for boring 0.2-0.5mm different pore sizes, then surface roughening treatment, washing, drying.
B, sponge roller is added in deionized water or distilled water, flexible base board is then passed through into sponge roller, in copper face
On be uniformly coated with water membrane.
C, 100 DEG C of the pad pasting temperature of laminator, pressure 5.5Kg/cm2, speed 1.2m/min.
【Exposure】
Sample stands 15min or more after pad pasting, is exposed, is used using the holy science and technology M-552 type parallel exposing machines of will
41 rank exposure guide rules of stouffer measure exposure lattice number, and exposure lattice number control is in 16-22 lattice, exposure energy 25-60mJ/cm2。
【Development】
Exposed sample stands 15min or more, 30 DEG C of development temperature, pressure 1.2Kg/cm2, developer solution is the carbon of 1%wt
Acid sodium aqueous solution, developing time are 1.5-2.0 times of minimum developing time, wash, dry after development.
【Acid etching】
Acid etching, etching solution are copper chloride (CuCl2)/hydrochloric acid (HCL) system, 50 DEG C of etch temperature, pressure 1.2Kg/
cm2, etching solution proportion 1.20-1.30g/mL, concentration of hydrochloric acid 1.5mol/L, copper ion concentration 120-160g/L.
【Move back film】
Alkalinity moves back film, and it is NaOH to move back film liquid, moves back 50 DEG C of film temperature, pressure 1.2Kg/cm2, membrane concentration 3-5wt% is moved back, is moved back
The film time is 1.5-2.0 times that minimum moves back the film time, moves back washing, drying after film.
【Move back the evaluation of film crack conditions】
The flexible base board after film, the 3M adhesive tapes junction of flexible base board and hard directing plate are moved back in observation, and whether dry film moves back film
Totally.
○：It is clean to move back film, noresidue；
△：Substantially it is clean to move back film, there is a small amount of residual；
×：It is unclean to move back film, there are a large amount of residuals.
【Move back film speed evaluation】
It moves back the film time by test and moves back film speed to evaluate, it is shorter to move back the film time, and it is faster to move back film speed.
○：Move back the film time 10-25 seconds；
△：Move back the film time 25-40 seconds；
×：Move back the film time>40 seconds.
【Move back the evaluation of film chip size】
1 piece of flexible base board after pad pasting, exposure, development is taken, the square of 5*5cm is cut into, is put into and is filled 100mL and move back film
In the beaker of liquid (concentration 3wt%, temperature 50 C), after magnetic agitation 1min, film chip size is moved back in observation.
○：Chip size 5-15mm；
△：Chip size 15-30mm；
×：Chip size>30mm.
【The evaluation of resolution ratio】
Using Line/Space=10/10-100/100 μm of equal line-spacings, etc. the photomask of line widths wiring pattern exposed
Photodevelopment is observed after washing drying using magnifying glass.
○：Resolution ratio 20-30um；
△：Resolution ratio 30-40um；
×：Resolution ratio>40um.
【The evaluation of adhesive force】
Using Line/Space=n/400 μm (n ranges from 15 to 51, equal line-spacings, different line width wirings incrementally 3) every time
The photomask of pattern is exposed development and is observed using magnifying glass after washing drying.
○：Adhesive force 20-30um；
△：Adhesive force 30-40um；
×：Adhesive force>40um.
【Flexible evaluation】
After pad pasting, exposure, development, by flexible parent metal doubling from different perspectives 20 times, whether observation dry film cracks, and statistics is opened
Number is split, with digital representation as a result, numerical value is smaller to illustrate that dry film flexibility is better.
○：Dry film cracks 0 time after doubling；
△：Dry film cracks 1-5 times after doubling；×：Dry film cracks for 5 times or more after doubling.
Evaluation result is shown in Table 3
It is can be found that by embodiment 1-6 and the comparison of comparative example 1-6：The double bond of photo polymerization monomer is rubbed in embodiment 1-6
You measure within the scope of 0.5-2.0m mol/g resin combinations, and the parts by weight of ethylene oxide-propylene oxide block copolymer
Within the scope of 0.1-10.0, from the point of view of test result, move back that film fracture is clean, moves back that film speed is fast, it is moderate to move back film chip size, and
Resolution ratio, adhesive force and flexibility evaluation are excellent.In comparative example 1-6, from the point of view of test result, film properties and resolution ratio, attached are moved back
Putting forth effort performance cannot take into account.In comparative example 1, ethylene oxide-propylene oxide block copolymer addition is 0, causes to move back film fracture
It is unclean, move back the decline of film speed；In comparative example 2-4, ethylene oxide-propylene oxide block copolymer parts by weight are more than 10.0, attached
Put forth effort wretched insufficiency, while resolution ratio declines；In comparative example 5, ethylenical unsaturated double bonds mole is less than in photo polymerization monomer
0.5m mol/g resin combinations, resin combination crosslink density is insufficient, leads to resolution ratio and adhesive force wretched insufficiency；Comparative example
In 6, ethylenical unsaturated double bonds mole is higher than 2.0m mol/g resin combinations in photo polymerization monomer, and resin combination crosslinking is close
Height is spent, it is unclean to lead to move back film fracture, moves back the decline of film speed.
It is unsaturated double by olefinic in the dosage and photo polymerization monomer of regulation and control ethylene oxide-propylene oxide block copolymer
Key mole, the present invention obtained by resin combination be used as dry film photoresist when, have move back film easy fracture, move back film chip size
It is moderate, move back the characteristics such as film speed is fast, while circuit resolution ratio, adhesive force and flexibility are excellent, it is thus possible to be pasted using wet method
When the flexible printed circuit board manufacture of membrane process, membrane efficiency is moved back in raising, and then improves production efficiency and product yield.
Claims (10)
1. a kind of photosensitive polymer combination, which is characterized in that the described resin combination includes：The bonding of 30-70 parts by weight
Agent polymer, the photo polymerization monomer of 10-50 parts by weight, the photoinitiator of 0.5-10.0 parts by weight and 0.1-10.0 parts by weight add
Add agent etc..Wherein, ethylenical unsaturated double bonds mole is 0.5-2.0m mol/g resin combinations in the photo polymerization monomer, is added
Add epoxy ethane-epoxy propane block copolymerization shown in general formula (I) or the general formula (II) containing 0.1-10.0 parts by weight in agent
Object.
In formula (I), x1, y1 and z1 are separate positive integer, and 7≤x1+y1+z1≤227.
In formula (II), x2, y2 and z2 are separate positive integer, and 7≤x2+y2+z2≤227.
2. according to photosensitive polymer combination shown in claims 1, which is characterized in that preferably comprised in the additive
Ethylene oxide-propylene oxide block copolymer shown in 1.0-7.0 parts by weight general formula (I) or general formula (II)；The general formula (I)
Shown in ethylene oxide-propylene oxide block copolymer preferably 17≤x1+y1+z1≤200；Epoxy shown in the general formula (II)
Oxide-propylene oxide block copolymer preferably 17≤x2+y2+z2≤200.
3. according to photosensitive polymer combination shown in claims 1, which is characterized in that the photo polymerization monomer is vinyl
Undersaturated monomer.
4. according to photosensitive polymer combination shown in claims 3, which is characterized in that the photo polymerization monomer can be by
(methyl) lauryl acrylate, (methyl) octadecyl acrylate, nonyl phenol acrylate, ethoxyquin (the third oxidation) nonyl
Phenol acrylate, isobornyl thiocyanoacetate, acrylic acid tetrahydrofuran methyl esters, bisphenol-A two (methyl) acrylate, ethoxyquin (the third oxidation)
Bisphenol-A two (methyl) acrylate, polyethylene glycol (propylene glycol) two (methyl) acrylate, ethoxyquin (the third oxidation) neopentyl glycol
Diacrylate, trimethylolpropane tris (methyl) acrylate, ethoxyquin (the third oxidation) trimethylolpropane tris (methyl) third
Olefin(e) acid ester, pentaerythritol triacrylate, pentaerythritol tetraacrylate, Dipentaerythritol Pentaacrylate, dipentaerythritol
One or more compositions in six acrylate.
5. according to photosensitive polymer combination shown in claims 1, which is characterized in that the photoinitiator is selected from 2,4,5-
Triarylimidazoles dimer and its derivative, thioxanthones, benzoin phenyl ether, benzophenone, benzoin methyl ether, N, N'- tetra-
Methyl -4,4'- diaminobenzophenones, N, N'- tetraethyl -4,4'- diaminobenzophenones, 4- methoxyl group -4'- dimethylaminos
Base benzophenone, 2- benzyl -2- dimethylaminos -1- (4- morpholino phenyls)-butanone, 2- ethyl hydrazine, phenanthrenequione, 2- tertiary butyls
Anthraquinone, prestox anthraquinone, 1,2 benzae thracene quinone, 2,3- benzos anthraquinone, 2,3- diphenyl anthraquinone, 1- chloroanthraquinones, 2-methylanthraquinone,
1,4- naphthoquinones, 9,10- phenanthrenequione, 2,3- dimethyl anthraquinone, benzoin methyl ether, benzoin ethyl ether, styrax phenyl ether, benzil two
Acridine derivatives, the N- phenyl such as the benzil derivatives such as methyl ketal, 9- phenylacridines, 1,7- bis- (9,9'- acridinyls) heptane
Glycine, coumarin series compounds, oxazole based compound；The 2,4,5- triarylimidazoles dimer and its derivative include 2-
(Chloro-O-Phenyl) -4,5- diphenyl-imidazoles dimer, two (methoxyphenyl) imidazole dimers of 2- (Chloro-O-Phenyl) -4,5-, 2-
(o-fluorophenyl) -4,5- diphenyl-imidazoles dimer, 2- (o-methoxyphenyl) -4,5- diphenyl-imidazoles dimer, 2- are (to first
Phenyl) -4,5- diphenyl-imidazole dimers.
6. according to photosensitive polymer combination shown in claims 5, which is characterized in that the photoinitiator preferably 2,2 ',
4- tri- (2- chlorphenyls) -5- (3,4- Dimethoxyphenyls) -4 ', 5 '-diphenyl -1,1 '-diimidazole.
7. according to photosensitive polymer combination shown in claims 1, which is characterized in that described adhesive polymer is by insatiable hunger
It being copolymerized to obtain with carboxylic acid and vinyl compound, polymer acid number is in 100-300mg KOH/g resins, weight average molecular weight 30,
000-150,000。
8. according to photosensitive polymer combination shown in claims 7, which is characterized in that the preferred 100- of polymer acid number
300mg KOH/g resins, weight average molecular weight preferably 30,000-150,000；The more preferable 120-200mg of polymer acid number
KOH/g resins, weight average molecular weight more preferable 40,000-100,000.
9. the photosensitive polymer combination described in a kind of claims 1 is used as the purposes of dry film photoresist, which is characterized in that should
Purposes is specifically, the dry film photoresist can carry out pad pasting, 80-110 DEG C of pad pasting temperature, pressure 4.0-7.0Kg/ with wet processing
cm2, speed 1.0-3.0m/min.
10. the photosensitive polymer combination described in a kind of claims 1 is used as the purposes of dry film photoresist, which is characterized in that
The purposes moves back film pressure 0.3-2.0Kg/cm specifically, the dry film photoresist can carry out moving back film under the conditions of Low-pressure spray2。
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| CN110941140A (en) * | 2018-09-21 | 2020-03-31 | 旭化成株式会社 | Photosensitive resin composition |
| CN111796483A (en) * | 2020-07-16 | 2020-10-20 | 福斯特(安吉)新材料有限公司 | Resin composition, mixture, dry film resist and corresponding element |
| WO2021036538A1 (en) | 2019-08-29 | 2021-03-04 | 浙江福斯特新材料研究院有限公司 | Photosensitive resin composition and application thereof |
| JP2023500301A (en) * | 2019-12-31 | 2023-01-05 | コーロン インダストリーズ インク | Photosensitive resin composition and dry film photoresist, photosensitive element, circuit board, and display device using the same |
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