CN116199822B - Carboxyl-containing gold resinate and negative-tone photo-etching organic gold slurry and preparation method thereof - Google Patents
Carboxyl-containing gold resinate and negative-tone photo-etching organic gold slurry and preparation method thereof Download PDFInfo
- Publication number
- CN116199822B CN116199822B CN202310443217.9A CN202310443217A CN116199822B CN 116199822 B CN116199822 B CN 116199822B CN 202310443217 A CN202310443217 A CN 202310443217A CN 116199822 B CN116199822 B CN 116199822B
- Authority
- CN
- China
- Prior art keywords
- gold
- parts
- reaction
- organic
- resinate
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/38—Esters containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/44—Preparation of metal salts or ammonium salts
-
- 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
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
Abstract
A carboxyl group-containing gold resinate, represented by the formula (iii), which is prepared by reacting a copolymer of methacrylic acid and 2-methyl-2-thiopyranylmethyl acrylate with ammonium tetrachloroaurate; further, according to the mass parts, 35-60 parts of gold resinate containing carboxyl, 10-25 parts of photosensitive monomer, 1-5 parts of photoinitiator, 20-40 parts of organic solvent, 1-4 parts of organic metal salt and 0.01-0.1 part of polymerization inhibitor are dissolved and mixed uniformly to obtain negative photoetching organic gold slurry; the organic gold paste forms a fine conductive circuit after printing, leveling, prebaking, exposing, developing, drying and sintering, and can be used in high-resolution and miniaturized integrated circuits and components.
Description
Technical Field
The application belongs to the technical field of electronic paste for integrated circuit manufacturing, and relates to carboxyl-containing gold resinate and negative-tone photo-etching organic gold paste and a preparation method thereof.
Background
The requirements for miniaturization and light weight of microelectronic products promote the development of electronic packaging technology to the directions of high integration level and high packaging density, and the requirements for smaller conductor lines and line pitches in circuits and higher resolution are that. The ultimate resolution of screen printing is 40-50 mu m, and how to upgrade the printing process to achieve higher precision and resolution becomes the most important technical place in industry. Researchers have found that combining photolithography with printing processes is an effective solution to improve electrode accuracy. One of the schemes is to sinter the slurry on a substrate, then cover the photoresist on the surface, and obtain a fine electrode pattern through a series of processes such as photolithography (a thick film wiring technique [ J ]. Microelectronics, 2002 (06): 435-437) realizing a fine line width through photolithography). Another solution is to directly give the properties of the paste photoresist, uniformly smear the photosensitive metal paste on a plate, form a desired pattern by photolithography, and finally sinter the pattern (CN 201080027528.8). The photosensitive paste capable of directly performing photolithography is more advantageous than the scheme of sintering before photolithography. Currently, photolithography processes are more applied to thick film pastes.
The organic gold slurry (called as gold water) is prepared by using gold resinate as a main material, matching with related metal salt additives and matching with an organic carrier. Organogold slurries have been used for the decoration of glass and ceramics, and as the electronics industry evolves, they are increasingly being mined for their function as electrical conductors. And printing and sintering the organic gold slurry to form a submicron-level gold film layer. Compared with thick film gold paste, the organic gold paste can save noble metal, and has simple and convenient process, good printing quality and low production cost. However, the most widely used organometallic slurries today are used by screen printing, and as mentioned above, this process can encounter bottlenecks and challenges in application to smaller size components. There is literature (noble metals, 1996,17 (3): 38-39) that uses a sintering-followed photolithography process to achieve a resolution of less than 50 μm for the organogold paste printed wiring. However, from the viewpoint of practicality, development of a photosensitive organic gold paste having a photolithography property itself has been demanded.
Disclosure of Invention
In order to overcome the problems in the prior art, the application provides carboxyl-containing gold resinate, negative-tone photo-etching organic gold slurry and a preparation method thereof. After exposure, the organic gold sizing agent disclosed by the application generates a crosslinking reaction in an exposed area, and an unexposed area can be eluted by an alkaline developer. The pattern of the exposed areas after development is preserved, which belongs to negative tone lithography. Sintering the pattern after photoetching to obtain a fine conductive circuit.
Specifically, in a first aspect of the present application, there is provided a carboxyl group-containing gold resinate having a chemical formula shown in (iii):wherein n is 1 、n 2 、n 3 The sum of (2) is an integer of 50 to 300, n 1 And n 2 、n 3 The ratio of the sum is 1:9~5:5, where n 2 Can be 0, n 2 And n 3 The ratio of (2) is 0: 10-7: 3.
in a second aspect of the present application, there is provided a method for producing gold resinate containing carboxyl groups according to the first aspect of the present application, wherein in a preferred embodiment, the production process comprises the steps of:
step 1: preparing 2-methyl-2-thiopyranyl methyl acrylate, the chemical formula of which is shown as (i): dissolving potassium thiocyanate in water, dropwise adding ethanol solution of glycidyl methacrylate, extracting reaction liquid by using an extractant after the reaction is finished, washing and drying the extract, and purifying by column chromatography to obtain (i);step 2: preparing a copolymer of methacrylic acid and thiopyranylmethyl 2-methyl acrylate, the chemical formula of which is shown in (ii): dissolving methacrylic acid and 2-methyl-2-thiopyranyl methyl acrylate in toluene, dropwise adding toluene solution of azo-diisobutyl for reaction at 80 ℃, introducing nitrogen for protection in the reaction process, pouring the reaction solution into methanol after the reaction is finished, filtering, washing and drying to obtain (ii),wherein n is 1 And n 2 The sum of (2) is an integer of 50-300, n 1 And n 2 The ratio of (2) is 10: 90-50: 50;
step 3: manufacturing processGold resinate is prepared, and the chemical formula is shown as (iii): dissolving ammonium tetrachloroaurate in tetrahydrofuran, dropwise adding the tetrahydrofuran solution of (ii), pouring the reaction solution into ethanol after the reaction is finished, washing the precipitated jelly with hot water and ethanol for three times in sequence to obtain brown powder, filtering and drying to obtain gold resinate,wherein n is 1 、n 2 、n 3 The sum of (2) is an integer of 50 to 300, n 1 And n 2 、n 3 The ratio of the sum is 1:9~5:5, where n 2 Can be 0, n 2 And n 3 The ratio of (2) is 0: 10-7: 3.
in a preferred embodiment, in step 1, the molar ratio of potassium thiocyanate to glycidyl methacrylate is 3: 1-2: 1, the reaction time is 24-48 h, and the reaction temperature is 30-70 ℃; in step 2, the molar ratio of methacrylic acid to thiopyranylmethyl 2-methyl acrylate was 10: 90-50: 50. the molar ratio of the total of the two monomer moles to the azobisisobutyl was 300: 1-80: 1, the reaction time is 6-12 h, and the reaction temperature is 60-100 ℃; in step 3, the molar ratio of sulfur to gold is 3.5, calculated as atoms: 1-1.05: 1, the reaction time is 2-4 hours, and the reaction temperature is 40-65 ℃.
In a preferred embodiment, the weight average molecular weight of the copolymer prepared in step 2 is 10000-30000 and the molecular weight distribution is 1.5-3.0.
The carboxyl group-containing gold resinate prepared as described above can chemically react with an alkaline developer and is further soluble in water.
In a preferred scheme, the negative photoetching organic gold slurry comprises, by mass, 35-60 parts of carboxyl-containing gold resinate, 10-25 parts of photosensitive monomer, 1-5 parts of photoinitiator, 20-40 parts of organic solvent, 1-4 parts of organic metal salt and 0.01-0.1 part of polymerization inhibitor.
In a preferred embodiment, the photoactive monomer is selected from one or more of ethoxylated trimethylolpropane triacrylate, trimethylol triacrylate, hexanediol diacrylate and tripropylene glycol diacrylate; the photoinitiator is selected from one or more of acetophenone photoinitiators, oxime ester photoinitiators and acyl phosphine oxide photoinitiators; the organic solvent is selected from one or more of terpineol, turpentine, diethylene glycol butyl ether and dipropylene glycol monobutyl ether; an organometallic salt selected from one or more of palladium octoate and (pentamethylcyclopentadienyl) rhodium dicarbonate; the polymerization inhibitor is selected from one or more of p-hydroxyanisole, hydroquinone, 2, 6-tetramethyl piperidine-N-oxygen free radical.
According to a fourth aspect of the present application, there is provided a method for preparing a negative photoresist organogold slurry according to the third aspect of the present application, in a preferred embodiment, the method comprises the steps of: according to the mass portion, 35-60 portions of the carboxyl-containing gold resinate, 10-25 portions of the photosensitive monomer, 1-5 portions of the photoinitiator, 1-4 portions of the organic metal salt and 0.01-0.1 portion of the polymerization inhibitor are fully dissolved in 20-40 portions of the organic solvent and are further uniformly mixed to obtain the negative photoetching organic gold slurry.
In a fifth aspect of the present application, there is provided a fine conductive line, in a preferred embodiment, the conductive line is prepared by printing, leveling, prebaking, exposing, developing, drying, and sintering the negative photoresist slurry according to the third or fourth aspect of the present application.
The application has the beneficial effects that:
the carboxyl-containing gold resinate disclosed by the application can be subjected to chemical reaction with an alkaline developer, so that the gold resinate can be dissolved in water. Further, the carboxyl-containing gold resinate provided by the application, an organic solvent, a photosensitive monomer and a photoinitiator are dissolved and mixed uniformly according to a certain proportion to obtain the negative photoetching organic gold slurry.
The negative photoetching organic gold slurry has the function of negative photoresist, and the conductive circuit prepared by printing, leveling, prebaking, exposing, developing, drying and sintering has high resolution and can be applied to high-resolution and miniaturized integrated circuits and components.
Detailed Description
The technical scheme of the present disclosure is described in detail below with specific examples. The following embodiments may be combined with each other, and some embodiments may not be repeated for the same or similar concepts or processes.
The technical scheme disclosed by the application is that 2-methyl-2-thiopyranyl methyl acrylate is prepared firstly, and methacrylic acid and 2-methyl-2-thiopyranyl methyl acrylate are polymerized according to a certain proportion to obtain a copolymer containing carboxyl. The copolymer reacts with ammonium tetrachloroaurate to obtain carboxyl-containing gold resinate. Fully dissolving carboxyl-containing gold resinate, a photosensitive monomer, a photoinitiator, an organic metal salt and a polymerization inhibitor in an organic solvent, and uniformly mixing to obtain negative photoetching organic gold slurry. The negative photoetching organic gold sizing agent disclosed by the application has photosensitivity, and the photoinitiator in the sizing agent is subjected to photochemical reaction to generate free radical to initiate the crosslinking polymerization reaction of the monomer, so that an exposure area becomes insoluble. The unexposed area contains carboxyl, and is dissolved in water to be eluted after reacting with alkaline developer, so that the pattern of the light-transmitting area on the mask is transferred to the substrate. The polymerization inhibitor in the organic gold slurry is used for avoiding the failure of the organic gold slurry caused by polymerization reaction in the storage process, and the addition of the organic metal salt ensures that the sintered conductive circuit has good adhesive force with the substrate. The ceramic substrate is used as a base, and the organic gold paste is subjected to printing, leveling, prebaking, exposure, development, drying and sintering to obtain the fine conductive circuit.
The following describes the disclosure of the present application with reference to examples of production of carboxyl group-containing gold resinate, examples of production of organogold slurry, and test examples, but the present application is not limited thereto. In the examples described below, the reagents used were all commercially pure.
Example 1: preparation of gold resinate 1#
(1) Potassium thiocyanate (243 g,2.5 mol) was dissolved in 500mL of water in a three-necked flask equipped with mechanical stirring, with stirring. Glycidyl methacrylate (142 g,1 mol) was diluted with 1-fold volume of ethanol and added dropwise to an aqueous solution of potassium thiocyanate via a constant pressure dropping funnel over 1 hour. After reaction for 24 hours at 35 ℃, heating was stopped. The reaction solution was extracted with dichloromethane, and the extract was washed with water to neutrality. The extract was dried over anhydrous sodium sulfate overnight, filtered, and purified by column chromatography to give 109g of thiopyranylmethyl 2-methyl acrylate as a colorless liquid with a yield of 69% and a purity of 96.8% as characterized by liquid mass spectrometry.
(2) In a three-necked flask equipped with mechanical stirring, thermometer and reflux condenser, (5.38 g,0.0625 mol) methacrylic acid and (29.67 g,0.1875 mol) thiopyranyl methyl 2-acrylate were diluted in 200mL of toluene and kept stirring. (0.39 g,2.37 mmol) of azobisisobutyronitrile was dissolved in 20mL of toluene, and the solution was added dropwise to the monomer solution via a constant pressure funnel over about 60 minutes. And (3) reacting for 6 hours at 60 ℃, and introducing nitrogen in the reaction process. After the completion of the reaction, the reaction mixture was slowly poured into an equal volume of methanol and stirred slowly, and a white powder was precipitated. Reduced pressure filtration, methanol leaching, and drying at 50deg.C for 6h to obtain copolymer 1#33.3g, which has a weight average molecular weight of 13668 and a molecular weight distribution of 2.4 as characterized by gel permeation chromatography.
(3) Ammonium tetrachloroaurate (35.7 g,0.1 mol) was dissolved in 150mL of tetrahydrofuran in a three-necked flask equipped with mechanical stirring, thermometer and reflux condenser, and the solution was heated to 40 ℃. The copolymer 1# was weighed (20.56 g, sulfur-containing 0.11 mol) and dissolved in 100mL of tetrahydrofuran and added dropwise to a tetrahydrofuran solution of ammonium tetrachloroaurate through a constant pressure dropping funnel, and the dropping speed was controlled to be about 60 minutes. The reaction was continued for 2h. Brown suspended matter was formed during the reaction. After the reaction, the reaction solution was slowly poured into 250mL of ethanol, and stirred, and the brown suspension gradually agglomerated into a gum. After standing, the supernatant was decanted, and the gum was washed with 100mL of hot water, 100mL of ethanol, and 3 times in that order to give a brown powder. After drying at 40℃41.1g of carboxyl group-containing gold resinate powder was obtained, designated gold resinate # 1.
The acid value of the gold resinate No. 1 was 40.4mgKOH/g.
The gold content of the gold resinate 1# was calculated to be 38.7wt% after sintering at 600 ℃.
Example 2: preparation of gold resinate # 2
(1) Potassium thiocyanate (243 g,2.5 mol) was dissolved in 400mL of water in a three-necked flask equipped with mechanical stirring, with stirring. Glycidyl methacrylate (142 g,1 mol) was diluted with 1-fold volume of ethanol and added dropwise to an aqueous solution of potassium thiocyanate via a constant pressure dropping funnel over 1 hour. After reacting at 50℃for 36 hours, the heating was stopped. The reaction solution was extracted with dichloromethane, and the extract was washed with water to neutrality. The extract was dried over anhydrous sodium sulfate overnight, filtered, and purified by column chromatography to give 132g of thiopyranylmethyl 2-methyl acrylate as a colorless liquid with a yield of 83% and a purity of 97.4% as characterized by liquid mass spectrometry.
(2) In a three-necked flask equipped with mechanical stirring, thermometer and reflux condenser, (6.49 g,0.075 mol) methacrylic acid and (27.69 g,0.175 mol) thiopyranyl methyl 2-acrylate were diluted in 200mL toluene with stirring. (0.20 g,1.2 mmol) of azobisisobutyronitrile was dissolved in 20mL of toluene, and the solution was added dropwise to the monomer solution via a constant pressure funnel over about 60 minutes. And (3) reacting for 8 hours at 80 ℃, and introducing nitrogen in the reaction process. After the completion of the reaction, the reaction mixture was slowly poured into an equal volume of methanol and stirred slowly, and a white powder was precipitated. Reduced pressure filtration, methanol leaching, and drying at 50deg.C for 6h to obtain copolymer 2# 32.2g, which has a weight average molecular weight of 21225 and a molecular weight distribution of 2.7 as characterized by gel permeation chromatography.
(3) Ammonium tetrachloroaurate (35.7 g,0.1 mol) was dissolved in 150mL of tetrahydrofuran in a three-necked flask equipped with mechanical stirring, thermometer and reflux condenser, and the solution was heated to 50 ℃. The copolymer 2# was weighed (27.3 g, sulfur-containing 0.14 mol) and dissolved in 150mL of tetrahydrofuran and added dropwise to a tetrahydrofuran solution of ammonium tetrachloroaurate through a constant pressure dropping funnel, and the dropping speed was controlled to be about 60 minutes. The reaction was continued for 3 hours. Brown suspended matter was formed during the reaction. After the reaction was completed, the reaction solution was slowly poured into 300mL of ethanol, and stirred, and the brown suspension gradually agglomerated into a gum. After standing, the supernatant was decanted, and the gum was washed with 100mL of hot water, 100mL of ethanol, and 3 times in that order to give a brown powder. After drying at 40℃50.1g of gold resinate powder containing carboxyl groups was obtained, designated gold resinate # 2.
The acid value of the gold 2# resinate was 59.0mgKOH/g.
The gold content of the gold resinate 2# was calculated to be 33.8wt% after sintering at 600 ℃.
Example 3: preparation of gold resinate 3#
(1) Potassium thiocyanate (243 g,2.5 mol) was dissolved in 450mL of water in a three-necked flask equipped with mechanical stirring, with stirring. Glycidyl methacrylate (142 g,1 mol) was diluted with 1-fold volume of ethanol and added dropwise to an aqueous solution of potassium thiocyanate via a constant pressure dropping funnel over 1 hour. After 48 hours of reaction at 70 ℃, the heating was stopped. The reaction solution was extracted with dichloromethane, and the extract was washed with water to neutrality. The extract was dried over anhydrous sodium sulfate overnight, filtered, and purified by column chromatography to give 146g of thiopyranylmethyl 2-methyl acrylate as a colorless liquid with a yield of 92% and a purity of 97.9% as characterized by liquid mass spectrometry.
(2) In a three-necked flask equipped with mechanical stirring, thermometer and reflux condenser, (17.22 g,0.20 mol) methacrylic acid and (47.47 g,0.30 mol) thiopyranyl methyl 2-acrylate were diluted in 400mL toluene and kept stirring. (0.40 g,2.4 mmol) of azobisisobutyronitrile was dissolved in 20mL of toluene, and the solution was added dropwise to the monomer solution via a constant pressure funnel over about 60 minutes. The reaction is carried out for 12h at 90 ℃, and nitrogen is introduced in the reaction process. After the completion of the reaction, the reaction mixture was slowly poured into an equal volume of methanol and stirred slowly, and a white powder was precipitated. Reduced pressure filtration, methanol leaching, and drying at 50 ℃ for 6 hours in a vacuum drying oven to obtain copolymer 3# 60.2g, wherein the weight average molecular weight of the copolymer is 21260, and the molecular weight distribution is 2.8 by gel permeation chromatography.
(3) Ammonium tetrachloroaurate (35.7 g,0.1 mol) was dissolved in 150mL of tetrahydrofuran in a three-necked flask equipped with mechanical stirring, thermometer and reflux condenser, and the solution was heated to 65 ℃. Copolymer 3# was weighed (36.6 g, sulfur-containing 0.17 mol) and dissolved in 150mL of tetrahydrofuran and added dropwise to a tetrahydrofuran solution of ammonium tetrachloroaurate through a constant pressure dropping funnel, and the dropping speed was controlled to be about 60 minutes after completion of the addition. The reaction was continued for 4h. Brown suspended matter was formed during the reaction. After the reaction was completed, the reaction solution was slowly poured into 300mL of ethanol, and stirred, and the brown suspension gradually agglomerated into a gum. After standing, the supernatant was decanted, and the gum was washed with 100mL of hot water, 100mL of ethanol, and 3 times in that order to give a brown powder. After drying at 40℃56.8g of gold resinate powder containing carboxyl groups was obtained, designated gold resinate 3#.
The acid value of the golden 3# resinate was 94.9mgKOH/g.
The gold content of the gold resinate 3# was calculated to be 29.4wt% after sintering at 600 ℃.
Examples 4 to 9: preparation of organic gold slurry 1# -6# -
According to the formulation of Table 1, gold resinate, a photosensitive monomer, a photoinitiator, an organic metal salt and a polymerization inhibitor prepared in examples 1 to 3 were dissolved in an organic solvent, and sufficiently and uniformly stirred using a gravity stirrer to obtain a negative-working photolithography organic gold paste. Except gold resinate, the compounds used in the formulation are all commercially available analytically pure reagents.
In table 1, the abbreviations represent the compounds as follows:
907: 2-methyl-1- (4-methylsulfanylphenyl) -2-morpholin-1-one
369: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone
OXE-01:1- [4- (phenylsulfanyl) phenyl ] -1, 2-octanedione 2- (O-benzoyl oxime)
OXE-02:1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] ethanone 1- (O-acetyl oxime)
TPO: (2, 4, 6-trimethylbenzoyl) diphenyl phosphine oxide
TPO-L:2,4, 6-Trimethylbenzoyl phenylphosphonic acid ethyl ester
ETPTA: ethoxylated trimethylolpropane triacrylate
TMPTA: trimethylol triacrylate
TPGDA: tripropylene glycol diacrylate
HDDA: hexanediol diacrylate
Rh: dicarbonyl (pentamethylcyclopentadienyl) rhodium
Pd: palladium pivalate
TEMPO:2, 6-tetramethylpiperidine-N-oxyl radical
The following tests were performed on the organogold slurries obtained in examples 4-9:
(1) Viscosity: the viscosity of the organogold slurry was measured by a viscometer at 10rpm at 25 ℃;
(2) Printability: printing the organogold paste in table 1 on a ceramic substrate by 300 mesh screen printing, and observing the printing state;
(3) Leveling property: standing the printing film at room temperature for 10 minutes, and observing a leveling state;
(4) Lithographic performance: the printed film was baked at 125℃for 10 minutes after leveling, and then exposed to 365nm ultraviolet light through a 20 μm open film mask with an exposure energy of 500mj. The exposed samples were developed with a 2.38wt% aqueous solution of tetramethylammonium hydroxide sprayed onto the printed substrate at a pressure of 10N for 60 seconds. The developed substrate was dried at 60 c for 10 minutes to obtain a desired conductive trace pattern sample. After the circuit pattern sample is sintered in a muffle furnace (850 ℃ for 30 minutes), observing the line width (L), the line spacing (S), the existence of short circuit and whether the line is flat or not through a 50-time optical microscope;
(5) Sintered conductive thickness and resistivity: the resistance value R at both ends of the test line was measured by milliohmmeter, the test line pattern was l=4.5 cm, the line width d=20 μm, and the thickness h was measured by scanning electron microscope, and the calculation formula of the resistivity was ρ=r×d×h/L.
The test results are shown in Table 2.
In some of the undisclosed embodiments of the present application, the inventors found that when the acid value of gold resinate is more than 100mgKOH/g, the edge of the conductive line is jagged, broken, and when the acid value of gold resinate is less than 30mgKOH, development is difficult, resulting in shorting of electrodes and a decrease in resolution. When the weight average molecular weight of the copolymer for preparing gold resinate is less than 10000, saw teeth or even short lines appear at the edges of the conductive line, and when the weight average molecular weight of the copolymer for preparing gold resinate is more than 30000, entanglement of gold resinate increases, development becomes difficult, and the resolution of the electrode is lowered or even short circuits occur. When the ratio of the photoinitiator in the organic gold paste is lower than 1 part by mass, a higher exposure dose is required to enable the organic gold paste to generate photocrosslinking reaction, so that the production efficiency is reduced. When the ratio of the photoinitiator in the organic gold paste is higher than 5 parts by mass, the phenomenon that the photoinitiator is precipitated with the time is prolonged, and the storage stability of the photoetching organic gold paste is reduced. When the collocation of the carboxyl group-containing gold resinate, the photosensitive monomer, the organic solvent and the organic metal salt is out of the range defined by the present application, not only is it difficult to obtain an organic gold paste suitable for printing viscosity, but also the situation that the fine conductive line after lithography is not dense and the resolution is reduced is easily caused.
Other embodiments of the disclosure will be apparent to those skilled in the art from consideration of the specification and practice of the disclosure disclosed herein. This application is intended to cover any adaptations, uses, or adaptations of the disclosure following, in general, the principles of the disclosure and including such departures from the present disclosure as come within known or customary practice within the art to which the disclosure pertains. It is intended that the specification and examples be considered as exemplary only, with a true scope and spirit of the disclosure being indicated by the following claims.
Claims (8)
1. A carboxyl group-containing gold resinate is characterized in that the chemical formula is shown as (iii):
wherein n is 1 、n 2 、n 3 The sum of (2) is an integer of 50 to 300, n 1 And n 2 、n 3 The ratio of the sum is 1:9 to 5:5, where n 2 Can be 0, n 2 And n 3 The ratio of (2) is 0:10 to 7:3.
2. a process for the preparation of the gold carboxyl-containing resin acid according to claim 1, comprising the steps of:
step 1: preparing 2-methyl-2-thiopyranyl methyl acrylate, the chemical formula of which is shown as (i): dissolving potassium thiocyanate in water, dropwise adding ethanol solution of glycidyl methacrylate, extracting reaction liquid by using an extractant after the reaction is finished, washing and drying the extract, and purifying by column chromatography to obtain (i);
step 2: preparing a copolymer of methacrylic acid and thiopyranylmethyl 2-methyl acrylate, the chemical formula of which is shown in (ii): dissolving methacrylic acid and the 2-methyl-2-thiopyranyl methyl acrylate obtained in the step 1 in toluene, dropwise adding toluene solution of azo-diisobutyl, reacting at 80 ℃, introducing nitrogen for protection in the reaction process, pouring the reaction solution into methanol after the reaction is finished, filtering, washing and drying to obtain (ii),
wherein n is 1 And n 2 The sum of (2) is an integer between 50 and 300, n 1 And n 2 The ratio of (2) is 10: 90-50: 50;
step 3: preparing gold resinate, wherein the chemical formula of the gold resinate is shown as (iii): dissolving ammonium tetrachloroaurate in tetrahydrofuran, dropwise adding the tetrahydrofuran solution obtained in the step (ii), pouring the reaction solution into ethanol after the reaction is finished, washing the precipitated jelly with hot water and ethanol for three times in sequence to obtain brown powder, filtering and drying to obtain gold resinate,
wherein n is 1 、n 2 、n 3 The sum of (2) is an integer of 50 to 300, n 2 May be 0, n1: (n2+n3) is 10: 90-50: 50 N2: the ratio of n3 is 0:10 to 7:3.
3. a process for producing according to claim 2,
in step 1, the molar ratio of potassium thiocyanate to glycidyl methacrylate is 3: 1-2: 1, the reaction time is 24-48 h, and the reaction temperature is 30-70 ℃;
in step 2, the molar ratio of methacrylic acid to thiopyranylmethyl 2-methyl acrylate was 10: 90-50: 50, the molar ratio of the total number of moles of the two monomers to the azobisisobutyl is 300:1 to 80:1, the reaction time is 6-12 h, and the reaction temperature is 60-100 ℃;
in step 3, the molar ratio of sulfur to gold is 3.5, calculated as atoms: 1 to 1.05:1, the reaction time is 2-4 h, and the reaction temperature is 40-65 ℃.
4. The process according to claim 2 or 3, wherein the copolymer obtained in step 2 has a weight average molecular weight ranging from 10000 to 30000 and a molecular weight distribution ranging from 1.5 to 3.0.
5. A negative photoresist organogold slurry, which is characterized by comprising, by mass, 35-60 parts of carboxyl group-containing gold resinate prepared by the preparation method of claim 1 or any one of claims 2-4, 10-25 parts of photosensitive monomer, 1-5 parts of photoinitiator, 20-40 parts of organic solvent, 1-4 parts of organic metal salt and 0.01-0.1 part of polymerization inhibitor.
6. The negative tone photolithographic organic gold paste of claim 5, wherein,
the photosensitive monomer is selected from one or more of ethoxylated trimethylolpropane triacrylate, trimethylol triacrylate, hexanediol diacrylate or tripropylene glycol diacrylate;
the photoinitiator is selected from one or more of acetophenone photoinitiators, oxime ester photoinitiators or acyl phosphine oxide photoinitiators;
the organic solvent is selected from one or more of terpineol, turpentine, diethylene glycol butyl ether or dipropylene glycol monobutyl ether;
the organometallic salt is selected from palladium octoate and/or dicarbonyl (pentamethylcyclopentadienyl) rhodium;
the polymerization inhibitor is selected from one or more of p-hydroxyanisole, hydroquinone or 2, 6-tetramethyl piperidine-N-oxygen free radical.
7. A method of preparing a negative working photoresist slurry according to claim 5 or 6, comprising the steps of: according to the parts by weight, 35 to 60 parts of the carboxyl group-containing gold resinate prepared by the preparation method of claim 1 or any one of claims 2 to 4, 10 to 25 parts of the photosensitive monomer, 1 to 5 parts of the photoinitiator, 1 to 4 parts of the organic metal salt and 0.01 to 0.1 part of the polymerization inhibitor are fully dissolved in 20 to 40 parts of the organic solvent and are further uniformly mixed to obtain the negative photoetching organic gold slurry.
8. A conductive circuit, which is characterized in that the conductive circuit is prepared by printing, leveling, prebaking, exposing, developing, drying and sintering a negative photoetching organic gold slurry prepared by the preparation method of claim 5 or 6 or the negative photoetching organic gold slurry prepared by the preparation method of claim 7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310443217.9A CN116199822B (en) | 2023-04-24 | 2023-04-24 | Carboxyl-containing gold resinate and negative-tone photo-etching organic gold slurry and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310443217.9A CN116199822B (en) | 2023-04-24 | 2023-04-24 | Carboxyl-containing gold resinate and negative-tone photo-etching organic gold slurry and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116199822A CN116199822A (en) | 2023-06-02 |
| CN116199822B true CN116199822B (en) | 2023-08-15 |
Family
ID=86514954
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310443217.9A Active CN116199822B (en) | 2023-04-24 | 2023-04-24 | Carboxyl-containing gold resinate and negative-tone photo-etching organic gold slurry and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116199822B (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8603366D0 (en) * | 1985-02-12 | 1986-03-19 | Napp Systems Inc | Photosensitive resin composition |
| CN101463106A (en) * | 2009-01-04 | 2009-06-24 | 成都金桨高新材料有限公司 | Copolymer film forming resin containing benzoxazine structure and deep UV negativity chemical amplification type photo resist |
| CN106886128A (en) * | 2017-03-28 | 2017-06-23 | 深圳市道尔顿电子材料有限公司 | A kind of negative photoresist |
| CN111100237A (en) * | 2019-12-23 | 2020-05-05 | 无锡德贝尔光电材料有限公司 | High-refractive-index alkaline water soluble resin, preparation method and high-refractive-index photoresist |
| CN112735631A (en) * | 2020-12-21 | 2021-04-30 | 有研工程技术研究院有限公司 | Low-viscosity organic gold paste capable of being sintered on surface of circuit board substrate at low temperature |
| CN114349965A (en) * | 2021-12-27 | 2022-04-15 | 江南大学 | Preparation method of S-element-containing high-refractive-index optical resin |
| CN114350202A (en) * | 2022-01-21 | 2022-04-15 | 东莞市蓝邦电子五金材料有限公司 | Water-soluble photosensitive ink and preparation method and construction method thereof |
-
2023
- 2023-04-24 CN CN202310443217.9A patent/CN116199822B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8603366D0 (en) * | 1985-02-12 | 1986-03-19 | Napp Systems Inc | Photosensitive resin composition |
| CN101463106A (en) * | 2009-01-04 | 2009-06-24 | 成都金桨高新材料有限公司 | Copolymer film forming resin containing benzoxazine structure and deep UV negativity chemical amplification type photo resist |
| CN106886128A (en) * | 2017-03-28 | 2017-06-23 | 深圳市道尔顿电子材料有限公司 | A kind of negative photoresist |
| CN111100237A (en) * | 2019-12-23 | 2020-05-05 | 无锡德贝尔光电材料有限公司 | High-refractive-index alkaline water soluble resin, preparation method and high-refractive-index photoresist |
| CN112735631A (en) * | 2020-12-21 | 2021-04-30 | 有研工程技术研究院有限公司 | Low-viscosity organic gold paste capable of being sintered on surface of circuit board substrate at low temperature |
| CN114349965A (en) * | 2021-12-27 | 2022-04-15 | 江南大学 | Preparation method of S-element-containing high-refractive-index optical resin |
| CN114350202A (en) * | 2022-01-21 | 2022-04-15 | 东莞市蓝邦电子五金材料有限公司 | Water-soluble photosensitive ink and preparation method and construction method thereof |
Non-Patent Citations (1)
| Title |
|---|
| "New Aqueous Base Developable Photoresist for Lithographic Printing Plates Applications";A. M. El-Demerdash等;《Journal of applied polymer》;第118卷;第1933-1942页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116199822A (en) | 2023-06-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105694582B (en) | Photocuring solder resist ink | |
| CN1318915C (en) | Alkali development type photocurable composition and pattern of burned matter obtained from same | |
| JP3672105B2 (en) | Photosensitive conductive paste | |
| KR101120229B1 (en) | Conductive paste and electrode using the same | |
| KR100669725B1 (en) | A photosensitive paste composition | |
| JP4062805B2 (en) | Photosensitive conductive paste for firing and method for forming fine electrode pattern | |
| CN116199822B (en) | Carboxyl-containing gold resinate and negative-tone photo-etching organic gold slurry and preparation method thereof | |
| CN108181785B (en) | Nano silver wire photoresist and application thereof in manufacturing of touch screen device | |
| CN116199817B (en) | Boc-containing gold resinate and positive photo-etching organic gold slurry and preparation method thereof | |
| CN111929989B (en) | Photosensitive resin composition, preparation method thereof, photosensitive organic carrier and yellow light paste | |
| JP5515466B2 (en) | Electron emission source paste, electron emission source and electron emission device using the same | |
| JP3632868B2 (en) | Resin composition and cured product thereof | |
| JP2002082428A (en) | Alkali developable photosensitive paste composition | |
| KR102080863B1 (en) | Photocurable compositon and method for forming pattern | |
| JP3681016B2 (en) | Resin composition and cured product thereof | |
| JP3611478B2 (en) | Alkali development type photosensitive paste composition | |
| CN111978239A (en) | Compound and photosensitive resin composition | |
| KR101476498B1 (en) | Acrylate resin and chemically enhanced positive-photoresist composition comprising the same | |
| JP2013210498A (en) | Photosensitive conductive paste and conductive circuit | |
| JP4122621B2 (en) | Radiation-sensitive resin composition for producing inorganic shaped article, inorganic shaped article produced therefrom, and method for producing inorganic shaped article | |
| JPH1053433A (en) | Photosensitive paste | |
| KR20130111314A (en) | Conductive paste and conductive circuit | |
| KR101903889B1 (en) | Compound for photo-crosslinking agent, method for producing the same, and photosensitive paste comprising the same | |
| CN116199811B (en) | Polymer thioether-based gold resinate and organic gold slurry and preparation method thereof | |
| WO2018032967A1 (en) | 9-phenylacridine macromolecule photosensitizer, and preparing method 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 |