CN108490737B - Photosensitive resin composition and application thereof - Google Patents
Photosensitive resin composition and application thereof Download PDFInfo
- Publication number
- CN108490737B CN108490737B CN201810209258.0A CN201810209258A CN108490737B CN 108490737 B CN108490737 B CN 108490737B CN 201810209258 A CN201810209258 A CN 201810209258A CN 108490737 B CN108490737 B CN 108490737B
- Authority
- CN
- China
- Prior art keywords
- resin composition
- weight
- photosensitive resin
- ethoxylated
- acrylate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
-
- 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
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Materials For Photolithography (AREA)
- Manufacturing Of Printed Circuit Boards (AREA)
Abstract
The invention discloses a photosensitive resin composition and application thereof, the resin composition comprises 30-70 parts by weight of adhesive polymer, 10-50 parts by weight of photopolymerization monomer, 0.5-10.0 parts by weight of photoinitiator and 0.1-10.0 parts by weight of additive, the molar weight of olefinic unsaturated double bond in the photopolymerization monomer is 0.5-2.0m mol/g resin composition, and the additive contains ethylene oxide-propylene oxide block copolymer; according to the invention, by regulating and controlling the using amount of the ethylene oxide-propylene oxide block copolymer and the molar amount of the ethylenically unsaturated double bonds in the photopolymerization monomer, the prepared resin composition has the characteristics of easy film stripping and breakage, moderate film stripping fragment size, high film stripping speed and the like when being used as a dry film resist, and meanwhile, the circuit resolution, the adhesive force and the flexibility are excellent, so that the film stripping efficiency can be improved, and the production efficiency and the product yield are further improved.
Description
Technical Field
The invention belongs to the field of printed circuit boards, and relates to a photosensitive resin composition and application thereof.
Technical Field
The printed circuit board is an insulating board with a printed circuit, and is divided into three types of rigidity, flexibility and rigidity-flexibility combination according to hardness. The flexible circuit board is also called as a flexible circuit board, or a flexible board or an FPC for short, has the advantages of high wiring density, light weight, thin thickness, less wiring space limitation, high flexibility and the like, completely meets the development trend of light weight, thinness, shortness and smallness of electronic products, and is an effective solution for meeting the requirements of miniaturization and movement of electronic products. The FPC can be freely bent, wound and folded, can bear millions of dynamic bending without damaging the lead, can be randomly arranged according to the space layout requirement, and can be randomly moved and stretched in a three-dimensional space, so that the effect of integration of component assembly and lead connection is achieved. The FPC can greatly reduce the volume and the weight of electronic products, and is suitable for the development of the electronic products in the directions of high density, miniaturization and high reliability. Therefore, the method is widely applied to the fields of PC and peripheral products, automotive electronics, medical appliances, communication products, consumer electronics and the like.
In recent years, high-density FPCs have been developed rapidly, and the line density has been increased and the interlayer structure has been diversified and multilayered, so that the line manufacturing process faces more challenges. The film removing is a key process in the FPC manufacturing, the film removing cleanness of the board surface directly influences the production of the subsequent process, and the film removing speed influences the production efficiency. In the field production process, due to the reasons of thin thickness and easy bending and deformation of the FPC, in order to prevent the FPC from being folded in a machine and even scrapped due to clamping, two measures are usually taken, namely, a hard guide plate is added in front of the FPC, and the FPC and the hard guide plate are connected by an adhesive tape; secondly, the film-removing spraying pressure is reduced and controlled to be 0.3-2.0Kg/cm2Within the range.
However, both measures have adverse effects. Firstly, the photosensitive resin composition is not easy to break at the joint of the tape, which can cause incomplete film removal and influence the production of the subsequent process. Meanwhile, the film removing pressure is reduced, the film removing time is prolonged, and the production efficiency is reduced. Patent document CN1828111B discloses a photosensitive resin composition for plating resist used for performing 2 or more different electroless plating layers, which is excellent in plating resist and stripping property by controlling the total number of moles of reactive groups of ethylenically unsaturated groups in the resin composition. Patent document CN102144189B provides a photosensitive resin composition which is excellent in resolution, adhesion, and capping performance and also in peeling performance by adding ethylene oxide-modified polyoxyethylene (tris (1-phenylethyl)) phenyl ether, but no further studies have been made on the problem of film peeling of FPC.
Disclosure of Invention
The invention aims to provide a photosensitive resin composition and application thereof, aiming at overcoming the defects of the prior art.
The purpose of the invention is realized by the following technical scheme: a photosensitive resin composition, the resin composition comprising: 30-70 parts of adhesive polymer, 10-50 parts of photopolymerization monomer, 0.5-10.0 parts of photoinitiator and 0.1-10.0 parts of additive. Wherein the molar weight of the ethylenic unsaturated double bond in the photopolymerization monomer is 0.5-2.0mmol/g resin composition, and the additive contains 0.1-10.0 parts by weight of ethylene oxide-propylene oxide block copolymer shown in general formula (I) or general formula (II).
In the formula (I), x1, y1 and z1 are respectively independent positive integers, and 7 is less than or equal to x1+ y1+ z1 is less than or equal to 227.
In the formula (II), x2, y2 and z2 are respectively independent positive integers, and 7 is not less than x2+ y2+ z2 is not less than 227.
Further, the additive preferably contains 1.0 to 7.0 parts by weight of an ethylene oxide-propylene oxide block copolymer represented by the general formula (I) or the general formula (II); the ethylene oxide-propylene oxide block copolymer represented by the general formula (I) is preferably 17. ltoreq. x1+ y1+ z 1. ltoreq.200; the ethylene oxide-propylene oxide block copolymer represented by the general formula (II) is preferably 17. ltoreq. x2+ y2+ z 2. ltoreq.200.
Further, the photopolymerizable monomer is a vinyl unsaturated monomer.
Further, the photopolymerizable monomer is composed of one or more of lauryl (meth) acrylate, stearyl (meth) acrylate, nonylphenol acrylate, ethoxylated (propoxylated) nonylphenol acrylate, isobornyl ester, tetrahydrofuryl acrylate, bisphenol a di (meth) acrylate, ethoxylated (propoxylated) bisphenol a di (meth) acrylate, polyethylene glycol (propylene glycol) di (meth) acrylate, ethoxylated (propoxylated) neopentyl glycol diacrylate, trimethylolpropane tri (meth) acrylate, ethoxylated (propoxylated) trimethylolpropane tri (meth) acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate.
Further, the photoinitiator is selected from 2,4, 5-triarylimidazole dimer and derivatives thereof, thioxanthone, benzoin phenyl ether, benzophenone, benzoin methyl ether, N ' -tetramethyl-4, 4' -diaminobenzophenone, N ' -tetraethyl-4, 4' -diaminobenzophenone, 4-methoxy-4 ' -dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2-ethylanthraquinone, phenanthrenequinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1, 2-benzoanthraquinone, 2, 3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, and derivatives thereof, Benzil derivatives such as 1, 4-naphthoquinone, 9, 10-phenanthrenequinone, 2, 3-dimethylanthraquinone, benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether and benzil dimethyl ketal, acridine derivatives such as 9-phenylacridine and 1, 7-bis (9,9' -acridinyl) heptane, N-phenylglycine, coumarin compounds and oxazole compounds; the 2,4, 5-triaryl imidazole dimer and derivatives thereof include 2- (o-chlorophenyl) -4, 5-diphenyl imidazole dimer, 2- (o-chlorophenyl) -4, 5-di (methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4, 5-diphenyl imidazole dimer, 2- (o-methoxyphenyl) -4, 5-diphenyl imidazole dimer, and 2- (p-methoxyphenyl) -4, 5-diphenyl imidazole dimer.
Further, the photoinitiator is preferably 2,2 ', 4-tris (2-chlorophenyl) -5- (3, 4-dimethoxyphenyl) -4', 5 '-diphenyl-1, 1' -diimidazole.
Further, the binder polymer was obtained by copolymerizing an unsaturated carboxylic acid and a vinyl compound, and the polymer had an acid value of 100-300mg KOH/g resin and a weight average molecular weight of 30,000-150,000.
Further, the polymer preferably has an acid value of 100-300mg KOH/g resin and a weight average molecular weight of 30,000-150,000; the polymer acid value is more preferably 120-200mg KOH/g resin, and the weight average molecular weight is more preferably 40,000-100,000.
The invention also provides the application of the photosensitive resin composition as a dry film resist, and the application is specifically that the dry film resist can be pasted by a wet process, the pasting temperature is 80-110 ℃, and the pressure is 4.0-7.0Kg/cm2The speed is 1.0-3.0 m/min.
The invention also relates toThe application of the photosensitive resin composition as a dry film resist is provided, and specifically, the dry film resist can be stripped under the condition of low-pressure spraying, and the stripping pressure is 0.3-2.0Kg/cm2。
The invention has the beneficial effect that the technical problems in the prior art are solved by regulating and controlling the using amount of the ethylene oxide-propylene oxide segmented copolymer and the molar amount of the ethylenically unsaturated double bonds in the photopolymerization monomer. When the resin composition prepared by the invention is used as a dry film resist, the resin composition has the characteristics of easy film stripping fracture, moderate film stripping fragment size, high film stripping speed and the like, and meanwhile, the circuit resolution, the adhesive force and the flexibility are excellent, so that the film stripping efficiency can be improved when a flexible printed circuit board adopting a wet film pasting process is manufactured, and further, the production efficiency and the product yield are improved.
Detailed Description
The present invention provides a photosensitive resin composition for a dry film resist, the resin composition comprising: 30-70 parts of adhesive polymer, 10-50 parts of photopolymerization monomer, 0.5-10.0 parts of photoinitiator and 0.1-10.0 parts of additive.
The binder polymer of the present invention is preferably a carboxyl group-containing vinyl resin obtained by copolymerizing an unsaturated carboxylic acid and a vinyl compound. Examples of the unsaturated carboxylic acid include (meth) acrylic acid, crotonic acid, methacrylic acid, maleic anhydride, itaconic acid, and crotonic acid. Examples of the vinyl compound include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, benzyl (meth) acrylate, styrene, α -methylstyrene, hydroxystyrene, (meth) acrylamide, N-methylol-acrylamide, N-butoxymethyl-acrylamide, phenoxyethyl (meth) acrylate, (alkoxylated) nonylphenol (meth) acrylate, N-dimethyl (meth) acrylate, N-diethyl (meth) acrylate, ethyl (meth) acrylate, N-diethyl (meth) acrylate, N-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, benzyl (meth) acrylate, styrene, α -methylstyrene, hydroxystyrene, N-dimethyl (meth) acrylate, N-diethyl (meth) acrylate, ethyl (meth) acrylate, N-butyl (meth) acrylate, and (meth) acrylate, Propyl N, N-dimethyl (meth) acrylate, propyl N, N-diethyl (meth) acrylate, and the like. The carboxyl group-containing vinyl-based resin may be obtained by copolymerizing one or more of the above-mentioned unsaturated carboxylic acids and one or more of the above-mentioned vinyl compounds. The preparation method can use the known method, such as solution polymerization, suspension polymerization, etc.
In the present invention, (meth) acrylate means acrylate and methacrylate, and ethoxylated (propoxylated) acrylate means ethoxylated acrylate and ethoxylated propoxylated hybrid acrylate.
The acid value of the binder polymer component is preferably 100-300mgKOH/g resin, more preferably 120-200 mgKOH/g resin, from the viewpoint of both developing speed and developing solution resistance. The weight average molecular weight of the above binder polymer (as measured by Gel Permeation Chromatography (GPC) using a standard polystyrene calibration curve) is preferably 30,000-150,000, more preferably 40,000-100,000.
Examples of the ethylenically unsaturated monomer that is the photopolymerizable monomer of the present invention include lauryl (meth) acrylate, stearyl (meth) acrylate, nonylphenol acrylate, ethoxylated (propoxylated) nonylphenol acrylate, isobornyl ester, tetrahydrofurfuryl acrylate, bisphenol a di (meth) acrylate, ethoxylated (propoxylated) bisphenol a di (meth) acrylate, polyethylene glycol (propylene glycol) di (meth) acrylate, ethoxylated (propoxylated) neopentyl glycol diacrylate, trimethylolpropane tri (meth) acrylate, ethoxylated (propoxylated) trimethylolpropane tri (meth) acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate.
In the present invention, the molar amount of the ethylenically unsaturated double bond in the photopolymerizable monomer is from 0.5 to 2.0m mol/g of the resin composition. If the molar amount of the double bonds is less than 0.5m mol/g of the resin composition, the resolution and adhesion of the dry film resist may be significantly reduced; if the molar amount of the double bond is more than 2.0 mol/g of the resin composition, the crosslinking density of the photosensitive resin composition becomes too high, which affects film-releasing properties.
The photoinitiator of the invention contains 2,4, 5-triaryl imidazole dimer and derivatives thereof, examples thereof include 2- (o-chlorophenyl) -4, 5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4, 5-bis (methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4, 5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4, 5-diphenylimidazole dimer, and 2- (p-methoxyphenyl) -4, 5-diphenylimidazole dimer, and 2,2 ', 4-tris (2-chlorophenyl) -5- (3, 4-dimethoxyphenyl) -4', 5 '-diphenyl-1, 1' -diimidazole is preferable. Further, thioxanthone, benzoin phenyl ether, benzophenone, benzoin methyl ether, N ' -tetramethyl-4, 4' -diaminobenzophenone, N ' -tetraethyl-4, 4' -diaminobenzophenone, 4-methoxy-4 ' -dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2-ethylanthraquinone, phenanthrenequinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1, 2-benzoanthraquinone, 2, 3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1, 4-naphthoquinone, 9, 10-phenanthrenequinone, 2, 3-dimethylanthraquinone, methyl ether, 2, methyl ether, 2, methyl ether, 2, benzil derivatives such as benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether and benzil dimethyl ketal, acridine derivatives such as 9-phenylacridine and 1, 7-bis (9,9' -acridinyl) heptane, N-phenylglycine, coumarin-based compounds and oxazole-based compounds.
The additive of the present invention comprises an ethylene oxide-propylene oxide block copolymer represented by the general formula (I) or (II).
In the formula (I), x1, y1 and z1 are respectively independent positive integers, and 7 is not less than x1+ y1+ z1 is not less than 227.
In the formula (II), x2, y2 and z2 are respectively independent positive integers, and 7 is not less than x2+ y2+ z2 is not less than 227.
The ethylene oxide-propylene oxide block copolymer is preferably used in an amount of 0.1 to 10.0 parts by weight, more preferably 1.0 to 7.0 parts by weight, from the viewpoint of both the film-releasing property and the adhesion. If the weight part is less than 0.1, the film removing performance is obviously affected; if the weight ratio is more than 10.0, the adhesion of the photosensitive resin composition is remarkably lowered.
Examples of the ethylene oxide-propylene oxide block copolymer of the present invention include polypropylene glycol-block-polyethylene glycol-block-polypropylene glycol having average molecular weights of 2000, 2700 and 3300; polyethylene glycol-block-polypropylene glycol-block-polyethylene glycol with average molecular weights of 1100, 1900, 2000, 2800, 2900, 4400, 5800 and 8400, and the reagents are from Aldrich company.
In the present invention, a dye such as malachite green, a photo-coupler such as leuco crystal violet, a color-forming heat stabilizer, a plasticizer, a pigment, a filler, an antifoaming agent, a flame retardant, a stabilizer, a leveling agent, a peeling accelerator, an antioxidant, a fragrance, an image forming agent, a thermal crosslinking agent, and the like may be added as necessary.
The resin composition of the present invention may be dissolved in a solvent such as methanol, ethanol, isopropanol, acetone, methyl ethyl ketone, toluene, N-dimethylformamide, propylene glycol methyl ether acetate, or a mixed solvent of these solvents, as required.
The present invention will be further described with reference to the following examples, but the scope of the present invention is not limited to the examples.
Examples 1 to 6, comparative examples 1 to 6)
The components were mixed in proportion according to the formulations shown in tables 1 and 2 below, and 60 parts by weight of acetone was added thereto, followed by sufficient stirring until completely dissolved, to prepare a resin composition solution having a solid content of 40%. The film was uniformly coated on the surface of a PET film (thickness 15um) as a support film by a coater, and dried in an oven at 85 ℃ for 10min to form a dry film resist layer with a thickness of 20um, which was green under a yellow light. Then, a polyethylene film as a protective layer was laminated on the surface thereof to a thickness of 20 μm, thereby obtaining a 3-layer photosensitive dry film.
The adhesive polymer a in tables 1 and 2 was prepared by itself, and the main component was methacrylic acid/acrylic acid/methyl methacrylate/n-butyl methacrylate/lauryl acrylate/styrene 18/5/45/15/9/8(Mw 72,000) by a solution polymerization method.
Photopolymerizable monomer:
b-1: (8) ethoxylated nonylphenol acrylate, molecular weight 626 (Saedoma)
B-2: (9) ethoxylated dimethacrylate, molecular weight 598 (Meiyuan)
B-3: (3) ethoxylated (17) propoxylated dimethacrylate, molecular weight 1330 (Meiyuan)
B-4: (6) ethoxylated trimethylolpropane triacrylate, molecular weight 560 (Saedoma)
B-5: (3) ethoxylated trimethylolpropane triacrylate, molecular weight 428 (Saedoma)
Photoinitiator (2):
c-1: 2,2 ', 4-tris (2-chlorophenyl) -5- (3, 4-dimethoxyphenyl) -4', 5 '-diphenyl-1, 1' -diimidazole (Changzhou powerful new electronic material)
C-2: n-phenylglycine (Cydia chemistry)
Additive:
d-1: polypropylene glycol-block-polyethylene glycol-block-polypropylene glycol, average molecular weight 2700(Aldrich)
D-2: polyethylene glycol-block-polypropylene glycol-block-polyethylene glycol, average molecular weight 2000(Aldrich)
D-3: polyethylene glycol-block-polypropylene glycol-block-polyethylene glycol, average molecular weight 4400(Aldrich)
D-4: brilliant green pigment (Shanghai Bailingwei chemical technology Co., Ltd.)
D-5: leuco crystal violet (Shanghai Bailingwei chemical technology Co., Ltd.)
D-6: tribromomethyl phenyl sulfone (Shanghai ladder love chemical)
D-7: n, N-Diethylhydroxylamine (Shanghai Bailingwei chemical technology Co., Ltd.)
TABLE 1
TABLE 2
The sample preparation methods (including film attachment, exposure, development, acid etching, and film removal), the sample evaluation methods, and the evaluation results of the examples and comparative examples are described below.
[ Wet pasting film ]
a. Cutting a double-sided Flexible Copper Clad Laminate (FCCL) into a rectangle of 25 x 20cm, drilling small holes with different apertures of 0.2-0.5mm on a flexible substrate by using a laser drilling machine, and then performing surface roughening treatment, washing and drying.
b. Adding deionized water or distilled water into the sponge roller, then passing the flexible substrate through the sponge roller, and uniformly coating a layer of water film on the copper surface.
c. The film sticking temperature of the film sticking machine is 100 ℃, and the pressure is 5.5Kg/cm2The speed was 1.2 m/min.
[ Exposure ] to light
Standing the filmed sample for more than 15min, exposing with M-552 type parallel light exposure machine, measuring exposure lattice number with stouffer 41-stage exposure ruler, controlling exposure lattice number at 16-22 lattices, and exposing energy at 25-60mJ/cm2。
[ DEVELOPING ]
The exposed sample is kept stand for more than 15min at the developing temperature of 30 ℃ and the pressure of 1.2Kg/cm2The developing solution is 1 wt% sodium carbonate aqueous solution, the developing time is 1.5-2.0 times of the minimum developing time, and the developing solution is washed and dried.
[ acid etching ]
Acid etching with copper chloride (CuCl) as etching solution2) Hydrochloric acid (HCL) system, etching temperature 50 deg.C, pressure 1.2Kg/cm2The specific weight of the etching solution is 1.20-1.30g/mL, the concentration of hydrochloric acid is 1.5mol/L, and the concentration of copper ions is 120-160 g/L.
[ DEFILLING ] OF FILM
Alkaline film stripping is carried out, wherein the film stripping liquid is NaOH, the film stripping temperature is 50 ℃, and the pressure is 1.2Kg/cm2The concentration of the film stripping solution is 3-5 wt%, and the film stripping time is the minimum film stripping time1.5-2.0 times, and washing and drying after film stripping.
[ evaluation of film removal and fracture ]
And observing the flexible substrate after the film is removed, wherein the dry film is removed completely at the joint of the flexible substrate and the 3M adhesive tape of the hard guide plate.
O: the film is removed cleanly without residue;
and (delta): the film is basically removed cleanly, and a small amount of residue exists;
x: the film is not removed cleanly and has a large amount of residues.
[ evaluation of film-Release Rate ]
The film stripping speed is evaluated by testing the film stripping time, and the shorter the film stripping time is, the faster the film stripping speed is.
O: the film removing time is 10-25 seconds;
and (delta): the film removing time is 25-40 seconds;
x: the film stripping time was >40 seconds.
[ evaluation of size of film-releasing fragment ]
Cutting 1 piece of the flexible substrate subjected to film pasting, exposure and development into a square with the length of 5 x 5cm, putting the square into a beaker filled with 100mL of stripping liquid (the concentration is 3 wt%, and the temperature is 50 ℃), magnetically stirring for 1min, and observing the size of stripping fragments.
O: the size of the fragments is 5-15 mm;
and (delta): the size of the fragments is 15-30 mm;
x: chip size >30 mm.
[ evaluation of resolution ]
The resist was exposed and developed using a photomask having a wiring pattern with an equal Line pitch of 10/10 to 100/100 μm and an equal Line width, washed with water and dried, and then observed using a magnifying glass.
O: the resolution is 20-30 um;
and (delta): the resolution is 30-40 um;
x: resolution >40 um.
[ evaluation of adhesion ]
The resist was exposed and developed using a photomask having wiring patterns of equal Line pitch and different Line widths, in which Line/Space was n/400 μm (n ranged from 15 to 51, and was increased by 3 at a time), washed with water and dried, and then observed using a magnifying glass.
O: the adhesive force is 20-30 um;
and (delta): the adhesive force is 30-40 um;
x: the adhesion is >40 um.
[ evaluation of flexibility ]
After film pasting, exposure and development, folding the flexible base material for 20 times from different angles, observing whether the dry film cracks, counting the cracking times, and expressing the result by using a number, wherein the smaller the numerical value, the better the flexibility of the dry film is.
O: the dry film is cracked for 0 time after being folded;
and (delta): the dry film is cracked for 1-5 times after being folded; x: the dry film is cracked for more than 5 times after being folded in half.
The evaluation results are shown in Table 3
By comparing examples 1-6 with comparative examples 1-6, it can be found that: examples 1 to 6, in which the molar amount of double bonds of the photopolymerizable monomer was in the range of 0.5 to 2.0m mol/g of the resin composition and the parts by weight of the ethylene oxide-propylene oxide block copolymer was in the range of 0.1 to 10.0, from the test results, film removal was clean in breakage, fast in film removal speed, moderate in film removal chip size, and excellent in the evaluations of resolution, adhesion, and flexibility. In comparative examples 1 to 6, from the test results, the film removing property and the resolution and the adhesion property were not compatible. In comparative example 1, the addition amount of the ethylene oxide-propylene oxide block copolymer was 0, which resulted in incomplete film removal and breakage and a decrease in film removal rate; in comparative examples 2 to 4, when the weight part of the ethylene oxide-propylene oxide block copolymer exceeded 10.0, the adhesion was seriously insufficient and the resolution was reduced; in comparative example 5, in which the molar amount of the ethylenically unsaturated double bond in the photopolymerizable monomer was less than 0.5m mol/g of the resin composition, the resin composition had insufficient crosslinking density, resulting in serious insufficient resolution and adhesion; in comparative example 6, when the molar amount of the ethylenically unsaturated double bond in the photopolymerizable monomer was more than 2.0 mol/g of the resin composition, the crosslinking density of the resin composition was too high, resulting in incomplete film release and a decrease in film release rate.
By regulating and controlling the using amount of the ethylene oxide-propylene oxide block copolymer and the molar amount of the ethylenically unsaturated double bonds in the photopolymerization monomer, the resin composition prepared by the invention has the characteristics of easy film stripping breakage, moderate film stripping fragment size, high film stripping speed and the like when being used as a dry film resist, and has excellent line resolution, adhesive force and flexibility, so that the film stripping efficiency can be improved when a flexible printed circuit board adopting a wet film pasting process is manufactured, and the production efficiency and the product yield are further improved.
Claims (10)
1. A photosensitive resin composition, characterized in that the resin composition comprises: 30-70 parts by weight of adhesive polymer, 10-50 parts by weight of photopolymerization monomer, 0.5-10.0 parts by weight of photoinitiator and 0.1-10.0 parts by weight of additive; wherein the photo-polymerization monomer contains 0.5-2.0 mol of ethylenic unsaturated double bond in photo-polymerization monomer, and the additive contains 0.1-10.0 weight parts of ethylene oxide-propylene oxide block copolymer shown in general formula (I) or general formula (II) relative to the total solid mass of each gram of photosensitive resin composition;
in the formula (I), x1, y1 and z1 are respectively independent positive integers, and 7 is equal to or less than x1+ y1+ z1 is equal to or less than 227;
in the formula (II), x2, y2 and z2 are respectively independent positive integers, and 7 is not less than x2+ y2+ z2 is not less than 227;
the binder polymer is obtained by copolymerizing an unsaturated carboxylic acid and a vinyl compound.
2. The photosensitive resin composition according to claim 1, wherein the additive comprises 1.0 to 7.0 parts by weight of an ethylene oxide-propylene oxide block copolymer represented by the general formula (I) or the general formula (II); the ethylene oxide-propylene oxide block copolymer shown in the general formula (I) is 17-200 of x1+ y1+ z 1; the ethylene oxide-propylene oxide block copolymer shown in the general formula (II) is 17-200 of x2+ y2+ z 2.
3. The photosensitive resin composition according to claim 1, wherein the photopolymerizable monomer is a vinyl unsaturated monomer.
4. The photosensitive resin composition according to claim 3, wherein the photopolymerizable monomer is selected from the group consisting of lauryl acrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate, nonylphenol acrylate, ethoxylated nonylphenol acrylate, isobornyl ester, tetrahydrofuryl methacrylate, bisphenol A diacrylate, bisphenol A dimethacrylate, ethoxylated bisphenol A diacrylate, ethoxylated bisphenol A dimethacrylate, ethoxylated propoxylated bisphenol A diacrylate, ethoxylated propoxylated bisphenol A dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, polyethylene glycol propylene glycol diacrylate, polyethylene glycol propylene glycol dimethacrylate, ethoxylated neopentyl glycol diacrylate, and mixtures thereof, Ethoxylated neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, ethoxylated trimethylolpropane triacrylate, ethoxylated trimethylolpropane trimethacrylate, ethoxylated propoxylated trimethylolpropane triacrylate, ethoxylated propoxylated trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate.
5. The photosensitive resin composition according to claim 1, wherein the photoinitiator is selected from the group consisting of 2,4, 5-triarylimidazole dimer and derivatives thereof, thioxanthone, benzoin phenyl ether, benzophenone, benzoin methyl ether, N ' -tetramethyl-4, 4' -diaminobenzophenone, N ' -tetraethyl-4, 4' -diaminobenzophenone, 4-methoxy-4 ' -dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2-ethylanthraquinone, phenanthrenequinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1, 2-benzoanthraquinone, 2, 3-diphenylanthraquinone, anthraquinone, and derivatives thereof, 1-chloroanthraquinone, 2-methylanthraquinone, 1, 4-naphthoquinone, 2, 3-dimethylanthraquinone, benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether, benzil derivatives of benzil dimethyl ketal, 9-phenylacridine, acridine derivatives of 1, 7-bis (9,9' -acridinyl) heptane, N-phenylglycine, coumarin compounds, oxazole compounds;
the 2,4, 5-triaryl imidazole dimer and derivatives thereof include 2- (o-chlorophenyl) -4, 5-diphenyl imidazole dimer, 2- (o-chlorophenyl) -4, 5-di (methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4, 5-diphenyl imidazole dimer, 2- (o-methoxyphenyl) -4, 5-diphenyl imidazole dimer, and 2- (p-methoxyphenyl) -4, 5-diphenyl imidazole dimer.
6. The photosensitive resin composition according to claim 1, wherein the photoinitiator is 2,2 ', 4-tris (2-chlorophenyl) -5- (3, 4-dimethoxyphenyl) -4', 5 '-diphenyl-1, 1' -diimidazole.
7. The photosensitive resin composition of claim 1, wherein the binder polymer has an acid value of 100-300mg KOH/g resin and a weight average molecular weight of 30,000-150,000.
8. The photosensitive resin composition of claim 7, wherein the binder polymer has an acid value of 120-200mg KOH/g resin and a weight average molecular weight of 40,000-100,000.
9. Use of the photosensitive resin composition according to claim 1 as a dry film resist, particularly as a wet process for the dry film resistThe process is carried out by sticking film at 80-110 deg.C and 4.0-7.0Kg/cm2The speed is 1.0-3.0 m/min.
10. The use of the photosensitive resin composition according to claim 1 as a dry film resist, wherein the dry film resist is subjected to film removal under a low-pressure spraying condition, and the film removal pressure is 0.3 to 2.0Kg/cm2。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810209258.0A CN108490737B (en) | 2018-03-14 | 2018-03-14 | Photosensitive resin composition and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810209258.0A CN108490737B (en) | 2018-03-14 | 2018-03-14 | Photosensitive resin composition and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108490737A CN108490737A (en) | 2018-09-04 |
| CN108490737B true CN108490737B (en) | 2021-11-02 |
Family
ID=63339124
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810209258.0A Active CN108490737B (en) | 2018-03-14 | 2018-03-14 | Photosensitive resin composition and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108490737B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2020076945A (en) * | 2018-09-21 | 2020-05-21 | 旭化成株式会社 | Photosensitive resin composition |
| CN109856912A (en) * | 2019-03-11 | 2019-06-07 | 浙江福斯特新材料研究院有限公司 | A kind of high adhesion force photosensitive polymer combination |
| CN110471256B (en) * | 2019-08-29 | 2023-05-12 | 杭州福斯特电子材料有限公司 | Photosensitive resin composition |
| US11827781B2 (en) | 2019-08-29 | 2023-11-28 | Zhejiang First Advanced Material R&D Institute Co., Ltd. | Photosensitive resin composition and use thereof |
| JP7376712B2 (en) * | 2019-12-31 | 2023-11-08 | 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 |
| CN111796483B (en) * | 2020-07-16 | 2021-06-25 | 福斯特(安吉)新材料有限公司 | Resin composition, mixture, dry film resist and corresponding element |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000206691A (en) * | 1999-01-13 | 2000-07-28 | Asahi Chem Ind Co Ltd | New photopolymerizable composition |
| CN1500232A (en) * | 2001-03-29 | 2004-05-26 | 日立化成工业株式会社 | Method for mfg. printed wiring board and photosenstive resin compsn. to be used for it |
| CN105340062A (en) * | 2013-06-26 | 2016-02-17 | 佳能株式会社 | Photocurable composition and method for manufacturing optical module using same |
| CN105474094A (en) * | 2013-11-29 | 2016-04-06 | 旭化成电子材料株式会社 | Photosensitive resin element |
| CN105974737A (en) * | 2016-06-16 | 2016-09-28 | 杭州福斯特光伏材料股份有限公司 | Photosensitive resin composition |
| CN107219726A (en) * | 2017-06-27 | 2017-09-29 | 浙江福斯特新材料研究院有限公司 | A kind of resin combination and purposes |
-
2018
- 2018-03-14 CN CN201810209258.0A patent/CN108490737B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000206691A (en) * | 1999-01-13 | 2000-07-28 | Asahi Chem Ind Co Ltd | New photopolymerizable composition |
| CN1500232A (en) * | 2001-03-29 | 2004-05-26 | 日立化成工业株式会社 | Method for mfg. printed wiring board and photosenstive resin compsn. to be used for it |
| CN105340062A (en) * | 2013-06-26 | 2016-02-17 | 佳能株式会社 | Photocurable composition and method for manufacturing optical module using same |
| CN105474094A (en) * | 2013-11-29 | 2016-04-06 | 旭化成电子材料株式会社 | Photosensitive resin element |
| CN105974737A (en) * | 2016-06-16 | 2016-09-28 | 杭州福斯特光伏材料股份有限公司 | Photosensitive resin composition |
| CN107219726A (en) * | 2017-06-27 | 2017-09-29 | 浙江福斯特新材料研究院有限公司 | A kind of resin combination and purposes |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108490737A (en) | 2018-09-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108490737B (en) | Photosensitive resin composition and application thereof | |
| CN107219726B (en) | Resin composition and application | |
| JP6052440B2 (en) | Photosensitive resin composition, photosensitive element, resist pattern forming method, printed wiring board manufacturing method | |
| CN110471256B (en) | Photosensitive resin composition | |
| EP1678557A2 (en) | Photosensitive resin compositions and photosensitive dry films using the same | |
| KR101011319B1 (en) | Photosensitive resin composition, photosensitive element using same, method for forming resist pattern, and method for producing printed wiring board | |
| CN111965939B (en) | Photosensitive resin composition and dry film resist thereof | |
| CN109856912A (en) | A kind of high adhesion force photosensitive polymer combination | |
| CN111221219B (en) | Photosensitive resin composition and photosensitive dry film | |
| CN114716628B (en) | LDI photosensitive dry film and preparation method thereof | |
| JP2898143B2 (en) | Photosensitive liquid composition, photosensitive film and laminate | |
| JP4022004B2 (en) | Photosensitive resin composition and photoresist ink for production of printed wiring board | |
| CN113900355B (en) | Photosensitive resin composition and dry film resist laminate | |
| JP4147920B2 (en) | Photosensitive resin composition, photosensitive element using the same, resist pattern forming method, and printed wiring board manufacturing method | |
| WO2021036538A1 (en) | Photosensitive resin composition and application thereof | |
| CN112824973A (en) | Dry film resist laminate | |
| JP4238631B2 (en) | Photosensitive resin composition, photosensitive element using the same, resist pattern forming method, and printed wiring board manufacturing method | |
| JP4529752B2 (en) | Photosensitive resin composition, photosensitive element, resist pattern forming method and printed wiring board manufacturing method | |
| CN109062005B (en) | Photosensitive dry film | |
| JP2010160417A (en) | Photosensitive resin composition, and photosensitive element, method for forming resist pattern and method for manufacturing printed wiring board using the photosensitive resin composition | |
| CN113341649B (en) | Photosensitive resin composition and dry film resist | |
| JP2905622B2 (en) | Crosslinkable curable resin composition | |
| JP4241097B2 (en) | Photosensitive resin composition, photosensitive element using the same, resist pattern forming method, and printed wiring board manufacturing method | |
| JP4517257B2 (en) | Photosensitive resin composition, photosensitive element using the same, resist pattern manufacturing method, and printed wiring board manufacturing method | |
| JP2004279479A (en) | Photosensitive element, forming method of resist pattern using the same, and method for manufacturing printed wiring board |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20210816 Address after: 311300 room 212, building 1, No. 8, foster street, Jinbei street, Lin'an District, Hangzhou City, Zhejiang Province Applicant after: Hangzhou foster Electronic Materials Co.,Ltd. Address before: 311305 1235 Dayuan Road, Qingshanhu street, Lin'an City, Hangzhou City, Zhejiang Province Applicant before: HANGZHOU FIRST APPLIED MATERIAL Co.,Ltd. |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |