CN108121159B - Photosensitive resin composition and application thereof - Google Patents
Photosensitive resin composition and application thereof Download PDFInfo
- Publication number
- CN108121159B CN108121159B CN201611070578.XA CN201611070578A CN108121159B CN 108121159 B CN108121159 B CN 108121159B CN 201611070578 A CN201611070578 A CN 201611070578A CN 108121159 B CN108121159 B CN 108121159B
- Authority
- CN
- China
- Prior art keywords
- photosensitive resin
- resin composition
- meth
- acrylate
- branched alkyl
- 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
- C07C209/06—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms
- C07C209/10—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms with formation of amino groups bound to carbon atoms of six-membered aromatic rings or from amines having nitrogen atoms bound to carbon atoms of six-membered aromatic rings
-
- 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
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/28—Applying non-metallic protective coatings
- H05K3/285—Permanent coating compositions
- H05K3/287—Photosensitive compositions
Landscapes
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials For Photolithography (AREA)
Abstract
The invention discloses a photosensitive resin composition, which comprises (A) a binder polymer, (B) a photopolymerization monomer, (C) a photoinitiator and (D) a benzidine derivative shown as a general formula (I). The photosensitive resin composition has high sensitivity, high resolution and high adhesion under the light with the wavelength of 365-405nm, and has high solubility in a solvent, good compatibility and excellent application performance.
Description
Technical Field
The invention belongs to the technical field of photocuring, and particularly relates to a photosensitive resin composition, in particular to a photosensitive resin composition which is suitable for exposure by using 365-405nm wavelength light and application thereof in aspects of printed circuit boards, color televisions, liquid crystal display elements and the like.
Background
The ultraviolet curing technology is developed rapidly, has the advantages of high curing speed, less pollution, low cost and the like, and is widely applied to the fields of holographic recording, laser direct plate making, photocuring, laser stereolithography and the like. In recent years, the application of LED as a new light source in the field of light curing is attracting more and more attention, and the LED shows great application potential in the aspects of light output, work efficiency, cost, environmental protection and the like, and the development of products matched with the LED light source has become the focus of research of those skilled in the art.
365-. The existing ultraviolet curing system has low sensitivity to the wave band and insufficient applicability. The photosensitizer is added while the components in the photocuring system are adjusted, so that the method is an effective means for enhancing the sensitivity of the system to the LED light source.
Tertiary amine-based photosensitizers are a material commonly used in visible light photocuring systems to promote the efficiency of photocuring polymerization. The applicant researches and discovers that aromatic amine has strong absorption in a near ultraviolet region, the maximum absorption band of the aromatic amine is obviously red-shifted if an electron-donating conjugation effect occurs in the aromatic amine, generally speaking, the electron-donating conjugation effect of esters is more obvious than that of amides, and the electron-donating conjugation effect of esters is more obvious if phenyl or diphenyl is connected in the group. Chinese patent CN102844709A discloses the use of an N, N' -tetraarylbenzidine derivative in a photosensitive resin, but it was found that its solubility in a specific solvent is not satisfactory in the use, and a small amount of photosensitizer precipitates after the photosensitive resin composition is coated on a support film and dried.
Brief description of the invention
The invention aims to provide a photosensitive resin composition which has high sensitivity, high resolution and high adhesion under the light with the wavelength of 365-405nm, high solubility in a solvent and good compatibility.
Specifically, a photosensitive resin composition is characterized by comprising the following components:
(A) a binder polymer;
(B) a photopolymerizable monomer;
(C) a photoinitiator;
(D) a benzidine derivative represented by the general formula (I);
wherein R is1Is selected from C1-C10Is a straight or branched alkyl group of (a), optionally (optionally), wherein-CH2-may be substituted by oxygen, sulphur or phenylene;
R2and R3Each independently represents C1-C10Or a linear or branched alkyl group of (1), optionally, wherein-CH2-may be substituted by oxygen, sulphur or phenylene;
R4selected from hydrogen, C1-C10Straight or branched alkyl of, or C3-C10A cycloalkyl group of (a).
The present invention also relates to a photoresist film prepared by using the photosensitive resin composition, and a method for preparing a resist pattern and a printed circuit board using the photosensitive resin composition.
The photosensitive resin composition uses the benzidine derivative shown in the general formula (I) as the photosensitizer, so that the composition has very high sensitivity to light with the wavelength of 365-405nm, high resolution, good hole covering performance and excellent printing-out performance after exposure. The benzidine derivative represented by the general formula (I) has more excellent solubility in a solvent, and does not cause defects such as disconnection and short circuit of a wiring pattern due to the generation of precipitates on a resist pattern caused by low solubility of a photosensitizer and the failure of curing of a lower resin caused by the inhibition of the transmission of an optical fiber. The photoresist film prepared by the photosensitive resin composition has high resolution, excellent adhesiveness and stable photosensitivity, the photoresist pattern formed by the photoresist film has high precision and rapid and efficient pattern formation, and the prepared printed circuit board has stable yield and high qualification rate.
Detailed Description
As described above, the photosensitive resin composition of the present invention comprises (a) a binder polymer, (B) a photopolymerizable monomer, (C) a photoinitiator, and (D) a benzidine derivative represented by the general formula (I).
The components are specifically described below.
(A) Binder polymers
Examples of the binder polymer (a) used in the present invention include: one or a mixture of two or more of a (meth) acrylic polymer, a (meth) acrylate polymer, a styrene polymer, an epoxy polymer, an aliphatic urethane (meth) acrylate polymer, and an aromatic urethane (meth) acrylate polymer.
Among the above polymers, carboxyl group-containing polymers, particularly (meth) acrylate polymers obtained by copolymerizing (meth) acrylate, ethylenically unsaturated carboxylic acid and other copolymerizable monomers, are preferably used. The (meth) acrylic acid ester may be methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, furfuryl (meth) acrylate, or glycidyl (meth) acrylate, and these (meth) acrylic acid esters may be used alone or in combination of two or more kinds. The ethylenically unsaturated carboxylic acid is preferably acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, and particularly preferably acrylic acid or methacrylic acid. These ethylenically unsaturated carboxylic acids may be used alone or in combination of two or more. The other copolymerizable monomer is preferably (meth) acrylamide, n-butyl (meth) acrylate, styrene, vinylnaphthalene, (meth) acrylonitrile, vinyl acetate, or vinylcyclohexane, and these monomers may be used alone or in combination of two or more.
The weight average molecular weight of the binder polymer is preferably 7000-150000, more preferably 30000-120000. The acid value is preferably from 30 to 500mgKOH/g, more preferably 100-400 mgKOH/g.
(B) Photopolymerizable monomers
The photopolymerizable monomer (B) used in the present invention is not particularly limited in kind, and may be, for example, a monomer having one polymerizable unsaturated functional group, a monomer having two polymerizable unsaturated functional groups, and/or a monomer having three or more polymerizable unsaturated functional groups. These monomers may be used alone or in combination of two or more.
The monomer having one polymerizable unsaturated functional group may be 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, pentyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isooctyl (meth) acrylate, ethoxylated nonylphenol (meth) acrylate, polypropylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, and these monomers may be used alone or in combination of two or more.
The monomer having two polymerizable unsaturated functional groups may be tripropylene glycol di (meth) acrylate, propylene glycol polypropylene ether di (meth) acrylate, ethoxylated bisphenol a di (meth) acrylate, 1, 9-nonanediol di (meth) acrylate, 1, 10-decanediol di (meth) acrylate, ethoxylated polytetrahydrofuran glycol di (meth) acrylate, ethoxylated polypropylene glycol di (meth) acrylate, and these monomers may be used alone or in combination of two or more kinds.
The monomer having three or more polymerizable unsaturated functional groups may be trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexaacrylate, and these monomers may be used alone or in combination of two or more.
In the photosensitive resin composition of the present invention, the content of the (B) photopolymerizable monomer is 15 to 350 parts, preferably 30 to 300 parts, and most preferably 50 to 200 parts, relative to 100 parts by weight of the (a) binder polymer.
(C) Photoinitiator
The photoinitiator (C) used in the present invention may be selected from the group consisting of hexaarylbisimidazole derivatives, arone derivatives, oxime ester derivatives, anthraquinone derivatives, benzophenones, benzildimethylketals, triazine derivatives, and coumarin derivatives, and these photoinitiators may be used alone or in combination of two or more. Preferably, the photoinitiator is a hexaarylbisimidazole derivative.
The hexaarylbisimidazole derivative as the photoinitiator may be 2, 2 ' -bis (2, 3-dichlorophenyl) -4, 4 ', 5, 5 ' -tetrakis (3-methoxyphenyl) bisimidazole, 2 ' -bis (2, 3-dichlorophenyl) -4, 4 ', 5, 5 ' -tetrakis (4-methoxyphenyl) bisimidazole, 2 ' -bis (2, 4-dichlorophenyl) -4, 4 ', 5, 5 ' -tetrakis (3-methoxyphenyl) phenylbisimidazole, 2 ' -bis (2, 5-dichlorophenyl) -4, 4 ', 5, 5 ' -tetrakis (3-methoxyphenyl) bisimidazole, 2 ', 4, 4 ' -tetrakis (2-chlorophenyl) -5, 5 ' -bis (3-methoxyphenyl) bisimidazole, 2, 2 ', 4, 4 ' -tetrakis (2-chlorophenyl) -5, 5 ' -bis (2, 3-dimethoxyphenyl) bisimidazole, 2 ' -bis (2-chlorophenyl) -4, 4 ', 5, 5 ' -tetrakis (3, 4, 5-trimethoxyphenyl) bisimidazole, 2 ' -bis (2-chlorophenyl) -4, 5-bis (3-methoxyphenyl) -4 ', 5 ' -diphenylbisimidazole, preferably 2, 2 ' -bis (2, 3-dichlorophenyl) -4, 4 ', 5, 5 ' -tetrakis (3-methoxyphenyl) bisimidazole, 2 ' -bis (2, 5-dichlorophenyl) -4, 4 ', 5, 5 ' -tetrakis (3-methoxyphenyl) bisimidazole, 2, 2 ' -bis (2-chlorophenyl) -4, 5-bis (3-methoxyphenyl) -4 ', 5 ' -diphenylbisimidazole. These hexaarylbisimidazole derivatives may be used alone or in combination of two or more.
In the photosensitive resin composition of the present invention, the content of the (C) photoinitiator is 0.1 to 20 parts by weight, preferably 0.5 to 15 parts by weight, and more preferably 1 to 10 parts by weight, based on 100 parts by weight of the total amount of the (a) binder polymer and the (B) photopolymerizable monomer.
(D) Biphenylamine derivatives
The benzidine derivative used in the present invention has a structure represented by the general formula (I):
preferably, in the formula (I), R1Is selected from C1-C4Or a linear or branched alkyl group of (1), optionally, wherein-CH2-may be substituted by oxygen or sulphur; r2And R3Each independently represents C1-C4Linear or branched alkyl of (a); r4Selected from hydrogen, C1-C4Straight or branched alkyl of, or C3-C8A cycloalkyl group of (a).
The maximum absorption wavelength of the benzidine derivative shown in the general formula (I) is in the range of 365-405nm, and the molar absorption coefficients at the 365nm and the 405nm are both larger than 42000.
A method for synthesizing a benzidine derivative represented by the general formula (I) comprises the following steps:
(1) reacting the raw material a with the raw material b to obtain an intermediate a;
(2) reacting the intermediate a with the raw material c in an organic solvent containing a catalyst to obtain an intermediate b;
(3) carrying out catalytic reaction on the raw material d and the raw material e by using a catalyst under the protection of nitrogen to obtain an intermediate c;
(4) carrying out catalytic reaction on the intermediate b and the intermediate c by a catalyst under the protection of nitrogen to obtain a product;
the reaction equation is as follows:
knowing the above reaction scheme, the specific reaction conditions in steps (1) to (4) are readily determined by those skilled in the art.
The reaction of step (1) may be carried out in the absence of a catalyst and in the absence of a solvent. The reaction temperature varies slightly depending on the kind of the raw material, and is usually 80 to 100 ℃.
In the step (2), the catalyst may be sodium methoxide, sodium hydroxide, sodium ethoxide, potassium methoxide, potassium hydroxide, potassium ethoxide, or the like. The type of the organic solvent is not particularly limited as long as the reaction raw material can be dissolved and the reaction is not adversely affected, and examples thereof include acetone, acetonitrile, dichloromethane, and N, N-dimethylformamide. The reaction temperature varies slightly depending on the kind of the raw material, and is usually 10 to 20 ℃.
The reaction in step (3) is preferably carried out in an organic solvent system, and the type of solvent is not particularly limited as long as it can dissolve the reaction raw materials and does not adversely affect the reaction, and examples thereof include acetone, acetonitrile, dichloromethane, and toluene. The catalyst can be one or the combination of more than two of sodium hydroxide, sodium tert-butoxide, triphenylphosphine, tri-tert-butylphosphine and tetrakis (triphenylphosphine) palladium. The reaction temperature is generally from 70 to 100 ℃.
The reaction in step (4) is preferably carried out in an organic solvent system, and the type of solvent is not particularly limited as long as it can dissolve the reaction raw materials and does not adversely affect the reaction, and examples thereof include acetone, acetonitrile, dichloromethane, and toluene. The catalyst is selected from one or the combination of more than two of sodium hydroxide, sodium tert-butoxide, triphenylphosphine, tri-tert-butylphosphine and tetrakis (triphenylphosphine) palladium. The reaction temperature is usually 75 to 120 ℃.
In the photosensitive resin composition of the present invention, the content of the benzidine derivative represented by the general formula (I) is 0.01 to 1 part by weight, preferably 0.05 to 0.8 part by weight, and more preferably 0.1 to 0.5 part by weight, based on 100 parts by weight of the total amount of the binder polymer (a) and the photopolymerizable monomer (B).
In the photosensitive resin composition of the present invention, in addition to the above components (a), (B), (C), and (D), additives such as a colorant (e.g., crystal violet, malachite green lake, methyl violet, victoria blue, etc.), a plasticizer, an antioxidant, a thermal polymerization inhibitor, a solvent, a stabilizer, a defoaming agent, a flame retardant, and the like may be optionally added according to the application.
The invention also relates to a photoresist film, which comprises a support and a photosensitive resin layer formed on the support, wherein the photosensitive resin layer is composed of the photosensitive resin composition.
The present invention also relates to a method of forming a resist pattern, comprising the steps of:
(1) providing a photosensitive resin layer on a circuit-forming substrate, the photosensitive resin layer being composed of the photosensitive resin composition;
(2) a predetermined portion of the photosensitive resin layer is irradiated with light having a wavelength of 365 and 405nm, and after photocuring, a portion other than the predetermined portion is removed by development.
The method of providing the photosensitive resin layer on the substrate may be: coating a photosensitive resin composition (solution) on a substrate and drying the coating to form a photosensitive resin layer; alternatively, a photosensitive resin layer is formed by performing a lamination process on a substrate using a photosensitive resin laminate including a support, a photosensitive resin layer, and optionally a protective layer as needed. These are well known to those skilled in the art.
Further, the present invention relates to a method for manufacturing a printed wiring board, characterized in that a circuit-forming substrate including a resist pattern is produced by the above method for forming a resist pattern, and then etched or plated.
In addition to the above applications, the photosensitive resin composition of the present invention can be used in other photo-curing application fields including, but not limited to, photo-curing coatings, inks, photoresists, and the like.
Detailed Description
The present invention will be described in further detail with reference to specific examples, which should not be construed as limiting the scope of the present invention.
Preparation of component D, i.e. a benzidine derivative of the general formula (I)
Example 1:
(1) preparation of intermediate a1
140.5g of p-methyl benzyl chloride and 199.2g of triethyl phosphite are added into a 500ml four-mouth bottle, stirred and heated to 80-90 ℃, and reacted for 3 h. Controlling the content of p-methylbenzyl chloride in GC to be less than 1 percent, and finishing the reaction. Distilling at 90 ℃ under normal pressure to distill out chloroethane serving as a reaction by-product, continuously distilling under reduced pressure to distill out unreacted triethyl phosphite, cooling to 30 ℃ after no fraction is distilled out, and discharging 212g of material in the kettle, namely an intermediate a1, with the purity of 98%.
The structure of intermediate a1 was confirmed by LCMS.
Mass spectrometry was performed using the instrument software to obtain 243 and 244 molecular fragment peaks, which were 242 molecular weight, consistent with T +1 and T + 2.
(2) Preparation of intermediate b1
242.2g of intermediate a1, 140.6g of p-chlorobenzaldehyde and 800g of dichloromethane are added into a 2000mL four-neck flask, the mixture is stirred and dissolved to be clear, the temperature is controlled to be 10-20 ℃, 70.3g of potassium methoxide is added in batches, the reaction lasts for about 2h, the reaction is continued for 3h after the addition is finished, and the HPLC is followed until the raw material intermediate a1 disappears (HPLC: < 1%), and the reaction is finished. Slowly dropwise adding 400g of pure water, separating out a water layer, evaporating most of solvent under reduced pressure, adding 300g of methanol, separating out solid, performing suction filtration, rinsing with methanol, and drying to obtain 198g of solid, namely the intermediate b1 with the purity of 98%.
The structure of intermediate b1 was determined by LCMS and1H-NMR was confirmed.
The mass spectrometry obtains 229.5 and 230.5 molecular fragment peaks by means of instrument attached software, the molecular weight of the product is 228.5, and the product is consistent with T +1 and T + 2;
1H-NMR(CDCl3，500MHz)：2.3501-2.3588(3H，d)，6.9881-6.9954(2H，d)，7.0622-7.0692(2H，d)，7.2692-7.2768(2H，d)，7.3574-7.3665(2H，d)，7.4192-7.4278(2H，d)。
(3) preparation of intermediate c1
44.6g of 4, 4 '-dichlorobiphenyl, 108.2g of 2-ethyl-6-methylaniline and 200g of toluene are added into a 1000mL four-neck flask, 19.6g of sodium tert-butoxide, 18g of tri-tert-butylphosphine and 0.8g of tetrakis (triphenylphosphine) palladium are added under the protection of nitrogen, the temperature is raised to 80-85 ℃, the reaction is kept for 10 hours, and HPLC is controlled until the 4, 4' -dichlorobiphenyl and intermediate state monosubstitutes thereof are reacted completely (HPLC: < 0.1%). Filtering while hot, evaporating the solvent from the mother liquor under reduced pressure, adding 200g of normal hexane, cooling to 10 ℃, stirring for crystallization, and performing suction filtration to obtain 94g of intermediate c1 with the purity of 98.0%.
The structure of intermediate c1 was determined by LCMS and1H-NMR was confirmed.
The mass spectrometry obtains 421 and 422 molecular fragment peaks by means of instrument attached software, the molecular weight of the product is 420, and the product is matched with T +1 and T + 2;
1H-NMR(CDCl3，500MHz)：1.2401-1.2466(6H，t)，2.3511-2.3564(2H，d)，2.5891-2.5923(4H，q)，3.9928-4.0053(2H，s)，6.4521-6.4553(4H，t)，6.5202-6.5245(4H，t)，6.6290-6.6311(4H，t)，6.6832-6.6877(2H，t)，7.2315-7.2354(4H，d)。
(4) preparation of product 1
57g of intermediate b1, 42.0g of intermediate c1 and 150g of toluene are added into a 1000mL four-neck flask, 33g of sodium tert-butoxide, 52g of tri-tert-butylphosphine and 0.52g of tetrakis (triphenylphosphine) palladium are added under the protection of nitrogen, the temperature is raised to 80-85 ℃, the reaction is kept for 10 hours, and the HPLC is controlled until the raw material intermediate c1 and intermediate state monosubstitutes thereof are completely reacted (HPLC: < 0.1%). Filtering while hot, evaporating the solvent from the mother liquor under reduced pressure, adding 200g of normal hexane, cooling to 10 ℃, stirring for crystallization, and performing suction filtration to obtain 70.6g of product 1 with the purity of 99.2%.
Structure of product 1 by LCMS and1H-NMR was confirmed.
The mass spectrometry obtains 778 and 779 molecular fragment peaks by means of instrument attached software, the molecular weight of the product is 777, and the product is consistent with T +1 and T + 2;
1H-NMR(CDCl3，500MHz)：1.2401-1.2466(6H，d)，2.3511-2.3564(6H，d)，2.5891-2.5923(4H，d)，6.4521-6.4553(2H，d)，6.4623-6.4659(4H，q)，6.5202-6.5245(4H，q)，6.6290-6.6311(4H，d)，6.6832-6.6877(2H，d)，6.9908-6.9946(4H，q)，7.1089-7.1114(4H，d)，7.1756-7.1790(4H，q)，7.2315-7.2354(4H，q)，7.2622-7.2664(4H，q)，7.4235-7.4266(4H，q)。
example 2:
products 2 to 7 having the following structures were synthesized by the method of example 1.
Performance characterization
The application properties of the photosensitive resin composition of the present invention were evaluated by formulating an exemplary photosensitive resin composition.
Unless otherwise indicated, the parts of each component are parts by mass.
1. Preparation of Performance evaluation object
< preparation of photosensitive resin laminate >
A photosensitive resin composition having a composition shown in Table 1 and propylene glycol monoethyl ether acetate were sufficiently stirred, mixed, coated on the surface of a 19 μm-thick polyethylene terephthalate film as a support using a bar, uniformly coated, and then dried in a dryer at 95 ℃ for 4min to form a photosensitive resin layer having a thickness of 40 μm. Subsequently, a polyethylene film having a thickness of 23 μm was laminated as a protective layer on the surface of the photosensitive resin layer on which the polyethylene terephthalate film was not laminated, to obtain a photosensitive resin laminate.
< leveling of substrate surface >
As a substrate for sensitivity and resolution evaluation, a ketone-coated laminate treated with a jet-cleaning grinder under a spray pressure of 0.20MPa was prepared.
< lamination >
While peeling off the polyethylene film of the photosensitive resin laminate, the surface was flattened, and the laminate was laminated on a ketone-coated laminate preheated to 60 ℃ by a hot roll laminator at a roll temperature of 105 ℃ under a gas pressure of 0.35MPa and a lamination speed of 1.5 m/min.
< Exposure >
Exposure was performed by an h-ray type direct writing exposure apparatus (Digital Light Processing) with an exposure amount of 8 in a stepwise exposure table evaluated in terms of sensitivity as described below.
< development >
After peeling off the polyethylene terephthalate film, the film was developed with 2.38 mass% aqueous tetramethylammonium hydroxide at 23 ℃ for 2min to dissolve and remove the unexposed portion of the photosensitive resin layer, and then washed with ultrapure water for one minute. At this time, the minimum time required for the photosensitive resin layer of the unexposed portion to be completely dissolved is set as the minimum development time.
TABLE 1
Note: the names/compositions of the components denoted by the symbols in table 1 are shown in table 2.
TABLE 2
2. Performance evaluation method
(1) Compatibility test
The photosensitive resin compositions having the compositions shown in Table 1 were sufficiently stirred and mixed, and uniformly applied to the surface of a 19 μm-thick polyethylene terephthalate film as a support by using a bar coater. Drying at 95 deg.C for 4min to form photosensitive resin layer. Thereafter, the coated surface was visually inspected and classified as follows:
o: the coating surface is uniform;
solid content: undissolved matter was precipitated on the coated surface.
(2) Presence or absence of precipitates
The photosensitive resin composition and dichloroethane were prepared in a mass ratio of 1: 15, and after stirring to dissolve it, the resultant was left at room temperature (25 ℃ C.) for one day, and the presence or absence of precipitates was visually observed.
(3) Absorbance at 365nm and 405nm (Abs)
The absorbance of the photosensitive resin compositions to the exposure wavelength was measured separately using a UV spectrophotometer.
(4) Sensitivity evaluation at 365nm and 405nm wavelengths
The laminated substrate was exposed for 15min using a 21-step exposure table manufactured by Stouffer having a 21-step brightness change from transparent to black to evaluate its sensitivity. After exposure, development was performed for 2 times the minimum development time, and the following steps were performed according to the exposure amount of 8 in the step exposure table in which the resist film was completely left:
o: the exposure amount was 20mJ/cm2The following;
very good: the exposure amount was 20mJ/cm2-50mJ/cm2(not inclusive);
●: the exposure amount was 50mJ/cm2The above.
(5) Resolution evaluation at 365nm and 405nm wavelengths
The laminated substrate was exposed for 15min through a line pattern mask in which the widths of the exposed and unexposed portions were in a ratio of 1: 1, and then developed with a time 2 times the minimum development time, to normally form the minimum mask line width of the cured resist line as a resolution value. The following classification was performed:
o: resolution value is below 30 μm;
very good: resolution values of 30 μm to 50 μm (not inclusive);
●: the resolution value is 50 μm or more.
(6) Evaluation of adhesion at 365nm and 405nm wavelengths
The laminated substrate was exposed for 15min through a line pattern mask in which the widths of the exposed and unexposed portions were in a ratio of 1: 100, and then developed with a time 2 times the minimum development time to normally form the minimum mask line width of the cured resist line as an adhesion value. The following classification was performed:
o: the adhesion value is below 30 mu m;
very good: an adhesion value of 30 μm to 50 μm (not inclusive);
●: the adhesion value is 50 μm or more.
(7) Adhesion at 365nm and 405nm
A data pattern in which the exposure dose of 6 stages in a stepwise exposure table is used to directly aim at an exposure line width/line distance of 12.5/400-50/400 (um) is developed in a time 2 times the minimum development time, and the minimum value of the line width between line widths generated without generating snaking or chipping is evaluated.
3. Results of Performance evaluation
The results of the property evaluations are shown in Table 3.
TABLE 3
As can be seen from the evaluation results in Table 3, the photosensitive resin composition of the present invention (schemes 1-4) has good compatibility, high sensitivity, good resolution and adhesion, and high solubility in solvents, avoids the defects of disconnection, short circuit and the like of wiring patterns, and improves the process yield. In addition, since the photosensitive resin compositions of embodiments 1-4 have small differences in absorbance at 365-405nm, the difference in exposure amount (sensitivity) required for curing is small, and stable throughput can be obtained. For comparative examples 1 and 2, the sensitivity at 365nm and 405nm was different, and the difference in absorbance at 365-405nm was large, so that the difference in exposure amount required for curing was large, and it was difficult to obtain stable throughput; and the solubility is unstable, and there are significant differences in sensitivity, resolution, adhesion, and adhesion.
In conclusion, the photosensitive resin composition disclosed by the invention has very excellent application performance in the field of photocuring and has a very good application prospect.
Claims (10)
1. A photosensitive resin composition comprising the following components:
(A) a binder polymer selected from (meth) acrylate-based polymers obtained by copolymerizing (meth) acrylate, an ethylenically unsaturated carboxylic acid, and other copolymerizable monomers;
(B) a photopolymerizable monomer;
(C) a photoinitiator which is a hexaarylbisimidazole derivative;
(D) a benzidine derivative represented by the general formula (I);
wherein R is1Is selected from C1-C10Or a linear or branched alkyl group of (1), optionally, wherein-CH2-may be substituted by oxygen, sulphur or phenylene;
R2and R3Each independently represents C1-C10Or a linear or branched alkyl group of (1), optionally, wherein-CH2-may be substituted by oxygen, sulphur or phenylene;
R4selected from hydrogen, C1-C10Straight or branched alkyl of, or C3-C10Cycloalkyl groups of (a);
the maximum absorption wavelength of the benzidine derivative represented by the general formula (I) is in the range of 365-405nm, and the molar absorption coefficients at the wavelengths of 365nm and 405nm are both larger than 42000.
2. The photosensitive resin composition according to claim 1, wherein: (B) the photopolymerizable monomer is a monomer having one polymerizable unsaturated functional group, a monomer having two polymerizable unsaturated functional groups, and/or a monomer having three or more polymerizable unsaturated functional groups.
3. The photosensitive resin composition according to claim 1, wherein: in the general formula (I), R1Is selected from C1-C4Or a linear or branched alkyl group of (1), optionally, wherein-CH2-may be substituted by oxygen or sulphur; r2And R3Each independently represents C1-C4Linear or branched alkyl of (a); r4Selected from hydrogen, C1-C4Straight or branched alkyl of, or C3-C8A cycloalkyl group of (a).
4. A photoresist film comprising a support and a photosensitive resin layer formed on the support, wherein the photosensitive resin layer is composed of the photosensitive resin composition according to any one of claims 1 to 3.
5. A method of forming a resist pattern, comprising the steps of:
(1) providing a photosensitive resin layer on a circuit-forming substrate, the photosensitive resin layer being composed of the photosensitive resin composition according to any one of claims 1 to 3;
(2) a predetermined portion of the photosensitive resin layer is irradiated with light having a wavelength of 365 and 405nm, and after photocuring, a portion other than the predetermined portion is removed by development.
6. A method of manufacturing a printed circuit board, comprising: a circuit-forming substrate comprising a resist pattern obtained by the method for forming a resist pattern according to claim 5, which is then used for etching or plating.
7. The method for synthesizing a benzidine derivative represented by the general formula (I) according to claim 1, which comprises the steps of:
(1) reacting the raw material a with the raw material b to obtain an intermediate a;
(2) reacting the intermediate a with the raw material c in an organic solvent containing a catalyst to obtain an intermediate b;
(3) carrying out catalytic reaction on the raw material d and the raw material e by using a catalyst under the protection of nitrogen to obtain an intermediate c;
(4) carrying out catalytic reaction on the intermediate b and the intermediate c by a catalyst under the protection of nitrogen to obtain a product;
the reaction equation is as follows:
8. the method of synthesis according to claim 7, characterized in that: in the step (2), the catalyst is sodium methoxide, sodium hydroxide, sodium ethoxide, potassium methoxide, potassium hydroxide or potassium ethoxide.
9. The method of synthesis according to claim 7, characterized in that: in the step (3), the catalyst is one or a combination of more than two of sodium hydroxide, sodium tert-butoxide, triphenylphosphine, tri-tert-butylphosphine and tetrakis (triphenylphosphine) palladium.
10. The method of synthesis according to claim 7, characterized in that: in the step (4), the catalyst is selected from one or a combination of more than two of sodium hydroxide, sodium tert-butoxide, triphenylphosphine, tri-tert-butylphosphine and tetrakis (triphenylphosphine) palladium.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611070578.XA CN108121159B (en) | 2016-11-29 | 2016-11-29 | Photosensitive resin composition and application thereof |
| TW106139831A TWI643835B (en) | 2016-11-29 | 2017-11-17 | Photosensitive resin composition and the usage thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611070578.XA CN108121159B (en) | 2016-11-29 | 2016-11-29 | Photosensitive resin composition and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108121159A CN108121159A (en) | 2018-06-05 |
| CN108121159B true CN108121159B (en) | 2021-04-20 |
Family
ID=62223809
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611070578.XA Active CN108121159B (en) | 2016-11-29 | 2016-11-29 | Photosensitive resin composition and application thereof |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN108121159B (en) |
| TW (1) | TWI643835B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111752091B (en) * | 2019-03-29 | 2022-09-06 | 常州正洁智造科技有限公司 | Application of HABI mixed photoinitiator in UVLED photocuring |
| CN110531583B (en) * | 2019-09-14 | 2023-09-29 | 浙江福斯特新材料研究院有限公司 | Photosensitive resin composition and dry film resist |
| JPWO2023136105A1 (en) * | 2022-01-17 | 2023-07-20 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6455579B1 (en) * | 1999-03-09 | 2002-09-24 | Kabushiki Kaisha Hayashibara Seibutsu Kagaku Kenkyujo | Pyran derivatives |
| JP2006091488A (en) * | 2004-09-24 | 2006-04-06 | Kyocera Mita Corp | Image forming apparatus |
| CN101987823A (en) * | 2010-11-30 | 2011-03-23 | 天津市佰斯康科技有限公司 | N, N'-diphenyl-N-(9, 9-dimethyl-2-fluorenyl)-N'-(9, 9-dimethyl-7'-(2''-naphthyl)-2'-fluorenyl)-benzidine and synthesis method thereof |
| CN102844709A (en) * | 2010-04-15 | 2012-12-26 | 日合墨东株式会社 | Photosensitive resin composition, photoresist film using same, method for forming resist pattern, and method for manufacturing printed wiring board |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007045758A (en) * | 2005-08-10 | 2007-02-22 | Kyocera Mita Corp | Method of purifying diamine compound |
| JP5521800B2 (en) * | 2010-06-08 | 2014-06-18 | Ｊｓｒ株式会社 | Radiation-sensitive resin composition, cured film, method for forming cured film, and display element |
| JP5768556B2 (en) * | 2011-07-22 | 2015-08-26 | 三菱化学株式会社 | Electrophotographic photosensitive member, electrophotographic photosensitive member cartridge, and image forming apparatus |
| JP6232928B2 (en) * | 2013-10-30 | 2017-11-22 | 京セラドキュメントソリューションズ株式会社 | Electrophotographic photosensitive member and image forming apparatus |
| KR102279715B1 (en) * | 2014-05-09 | 2021-07-22 | 삼성전자주식회사 | Method of forming semiconductor device and the device |
-
2016
- 2016-11-29 CN CN201611070578.XA patent/CN108121159B/en active Active
-
2017
- 2017-11-17 TW TW106139831A patent/TWI643835B/en active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6455579B1 (en) * | 1999-03-09 | 2002-09-24 | Kabushiki Kaisha Hayashibara Seibutsu Kagaku Kenkyujo | Pyran derivatives |
| JP2006091488A (en) * | 2004-09-24 | 2006-04-06 | Kyocera Mita Corp | Image forming apparatus |
| CN102844709A (en) * | 2010-04-15 | 2012-12-26 | 日合墨东株式会社 | Photosensitive resin composition, photoresist film using same, method for forming resist pattern, and method for manufacturing printed wiring board |
| CN101987823A (en) * | 2010-11-30 | 2011-03-23 | 天津市佰斯康科技有限公司 | N, N'-diphenyl-N-(9, 9-dimethyl-2-fluorenyl)-N'-(9, 9-dimethyl-7'-(2''-naphthyl)-2'-fluorenyl)-benzidine and synthesis method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108121159A (en) | 2018-06-05 |
| TW201819352A (en) | 2018-06-01 |
| TWI643835B (en) | 2018-12-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6196363B2 (en) | Novel β-oxime ester fluorene compound, photopolymerization initiator containing the same, and photoresist composition | |
| CN101541837B (en) | Curable composition containing hydroxyl group-containing thiol compound and cured product thereof | |
| TWI406847B (en) | Oxime ester compound to used for photosensitive polymer composition | |
| JP6408715B2 (en) | Novel oxime ester derivative compound, photopolymerization initiator containing the same, and photoresist composition | |
| JP5450314B2 (en) | Photopolymerization initiator and photosensitive composition | |
| US8460853B2 (en) | Photosensitive resin composition, photosensitive element, resist pattern manufacturing method, and printed circuit board manufacturing method | |
| KR20130124215A (en) | Novel fluorene oxime ester compounds, photopolymerization initiator and photoresist composition containing the same | |
| CN103998422A (en) | Cyclopentadiketoxime ester and applications thereof | |
| KR101883164B1 (en) | Asymmetric dioxime ester compound and manufacturing method and use therof | |
| KR101892086B1 (en) | Oxime ester derivative compounds, photopolymerization initiator, and photosensitive composition containing the same | |
| CN108121159B (en) | Photosensitive resin composition and application thereof | |
| US20210198193A1 (en) | Trans, trans-diketone oxime ester isomer, manufacturing method thereof and application thereof | |
| CN105700293A (en) | Black photosensitive resin composition, black array and image display device comprising the same | |
| TWI688610B (en) | Curable resin composition, dry film, cured product and printed circuit board | |
| JP7465998B2 (en) | Ethoxy/propoxy modified pyrazoline organics, their use, photocurable compositions and photoresists | |
| TWI552981B (en) | Novel di-oxime ester compound and photopolymerization initiator and photoresist composition including the same | |
| CN110357989B (en) | Tertiary amine photosensitizer, preparation method thereof, photosensitive resin composition containing tertiary amine photosensitizer and application of photosensitive resin composition | |
| CN107765510B (en) | 9-phenylacridine macromolecular photosensitizer and preparation method and application thereof | |
| KR101824443B1 (en) | Novel fluorenyl oxime ester compounds, photopolymerization initiator and photoresist composition containing the same | |
| CN111221215A (en) | Photosensitive resin composition and application thereof | |
| KR102509606B1 (en) | Novel quinolinyl beta oxime ester derivative compound, photopolymerization initiator, and photoresist composition containing the same | |
| KR101991838B1 (en) | Novel 1,3-benzodiazole beta-oxime ester compound and composition comprising the same | |
| JPH11256088A (en) | Resin composition for alkali-soluble resist ink | |
| KR20030032822A (en) | Positive type photosensitive resist composition and use thereof |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |