CN116199817B - Boc-containing gold resinate and positive photo-etching organic gold slurry and preparation method thereof - Google Patents

Abstract

A gold resinate containing tert-butoxycarbonyl group, the chemical formula of which is shown as (iii), is prepared by reacting copolymer of tert-butyl methacrylate and 2-methyl-2-thiopyranylmethyl acrylate with ammonium tetrachloroaurate; further, according to the parts by weight, 35-60 parts of the gold resinate, 1-5 parts of the photoacid generator, 0.1-0.5 part of the sensitizer, 0.05-0.1 part of the acid diffusion inhibitor and 1-4 parts of the organic metal salt are dissolved in 30-60 parts of the organic solvent and fully and uniformly mixed to obtain positive photoetching organic gold slurry; the organic gold paste forms a fine conductive circuit after printing, leveling, pre-baking, exposing, post-baking, developing, drying and sintering, and can be used in high-resolution and miniaturized integrated circuits and components.

Description

Boc-containing gold resinate and positive photo-etching organic gold slurry and preparation method thereof

Technical Field

The application belongs to the technical field of electronic paste for integrated circuit manufacturing, and relates to gold resinate containing tert-butoxycarbonyl and positive 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 gold resinate and positive photo-etching organic gold slurry containing tert-butoxycarbonyl and a preparation method thereof. The tert-butoxy carbonyl in the gold resinate disclosed by the application is removed under the catalysis of acid to expose carboxyl, so that the gold resinate can be dissolved by an alkaline solution. The combination of the gold resinate containing t-butoxycarbonyl group with photoacid generator and other necessary components imparts photosensitive properties to the organogold slurry. The organic gold paste disclosed by the application is subjected to exposure, post-baking and development, the exposed area is eluted by the developer, the unexposed area is reserved, the organic gold paste belongs to positive photoetching, and a fine conductive line is obtained by sintering a pattern after photoetching.

Means for solving the problems:

in a first aspect of the present application, there is provided a t-butoxycarbonyl group-containing gold resinate having the formula (iii):wherein n is ₁ 、n ₂ The sum of (2) is an integer of 50 to 300, n ₁ And n ₂ The ratio range of (2): 8~5:5.

according to a second aspect of the application, there is provided a method for preparing gold resinate containing t-butoxycarbonyl according to the first aspect of the application, 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 tert-butyl methacrylate and thiopyranylmethyl 2-methyl acrylate, the chemical formula of which is shown as (ii): dissolving tert-butyl methacrylate and 2-methyl-2-thiopyranyl methyl acrylate in toluene, dropwise adding toluene solution of azo-diisobutyl, reacting at 80 ℃, introducing nitrogen for protection during the reaction, pouring the reaction solution into methanol after the reaction is finished, filtering, washing and drying to obtain (ii),wherein n is ₁ 、n ₂ The sum of (2) is an integer of 50 to 300, n ₁ And n ₂ The ratio range of (2) is 20: 80-50: 50;

step 3: preparing gold resinate as shown in a chemical formula (iii): dissolving ammonium tetrachloroaurate in tetrahydrofuran, dripping tetrahydrofuran solution of (ii), pouring the reaction solution into ethanol after the reaction is finished, washing the precipitated jelly with hot water and ethanol in sequence to obtain brown powder, filtering and drying to obtain gold resinate (iii),wherein n is ₁ 、n ₂ The sum of (2) is an integer of 50 to 300, n ₁ And n ₂ The ratio range of (2): 8~5:5.

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 t-butyl methacrylate 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: 1-80: 1, the reaction time is 6-12 h, and the reaction temperature is 60-100 ℃; in step 3, the mole ratio of sulfur to gold is 1, calculated as atoms: 1-1: 1.05, 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 gold resinate containing the tert-butoxycarbonyl group prepared by the method is easy to remove the tert-butoxycarbonyl group under the action of acid catalysis to expose carboxyl, and can be dissolved in alkaline developer.

In a third aspect of the present application, there is provided a positive-working photoresist slurry comprising, in parts by mass: 35-60 parts of the gold resinate containing tert-butoxycarbonyl according to the first or second aspect of the present application, 1-5 parts of photoacid generator, 0.1-0.5 part of sensitizer, 0.05-0.1 part of acid diffusion inhibitor, 30-60 parts of organic solvent and 1-4 parts of organic metal salt.

In a preferred embodiment, the photoacid generator is at least one selected from iodonium salt derivatives, sulfonium salt photoacid generators or oxime sulfonate photoacid generators; the acid diffusion inhibitor is at least one selected from trimethyl sulfonium hydroxide, tetrabutylammonium hydroxide or 2-phenylbenzimidazole; the sensitizer is selected from at least one of 2-ethylanthraquinone, N-ethylcarbazole or 2-isopropylthioxanthone; the organic solvent is selected from at least one of terpineol, turpentine, diethylene glycol butyl ether or dipropylene glycol monobutyl ether; the organometallic salt is selected from palladium octoate and/or rhodium dicarbonyl (pentamethylcyclopentadienyl).

According to a fourth aspect of the present application, there is provided a method for preparing the positive photoresist organogold slurry according to the third aspect of the present application, comprising the steps of: according to the mass portion, 35-60 portions of the resin acid gold containing the tert-butoxycarbonyl group, 1-5 portions of the photoacid generator, 0.1-0.5 portion of the sensitizer, 0.05-0.1 portion of the acid diffusion inhibitor and 1-4 portions of the organic metal salt are fully dissolved in 30-60 portions of the organic solvent and are further uniformly mixed to obtain the positive photoetching organic gold slurry.

In a fifth aspect, the present application provides a conductive circuit, which is prepared by printing, leveling, pre-baking, exposing, post-baking, developing, drying and sintering the positive photo-etching organic gold paste in the third or fourth aspect.

The application has the beneficial effects that:

the gold resinate containing the tert-butoxycarbonyl group disclosed by the application is easy to remove the tert-butoxycarbonyl group under the action of acid catalysis to expose carboxyl, and can be further dissolved in alkaline developer. Further, the gold resinate containing the tert-butoxycarbonyl group provided by the application is dissolved and uniformly mixed with an organic solvent, a photoacid generator, a sensitizer, an acid diffusion inhibitor and an organic metal salt according to a certain proportion to obtain the positive photoetching organic gold slurry.

The positive photoetching organic gold slurry has the function of positive photoresist, and the conductive circuit prepared by printing, leveling, pre-baking, exposing, post-baking, developing, drying and sintering has high resolution and can be applied to high-resolution and miniaturized integrated circuits and components.

Description of the embodiments

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 firstly prepared, and then tert-butyl methacrylate and 2-methyl-2-thiopyranyl methyl acrylate are polymerized according to a certain proportion to obtain a copolymer containing tert-butoxycarbonyl. The copolymer reacts with ammonium tetrachloroaurate to obtain gold resinate containing tert-butoxycarbonyl. Fully dissolving the gold resinate containing the tert-butoxycarbonyl, the photoacid generator, the sensitizer, the acid diffusion control agent and the organic metal salt in an organic solvent and uniformly mixing to obtain the positive photoetching organic gold slurry. The slurry disclosed by the application has photosensitivity, and the photoacid generator in an exposure area generates strong acid through photochemical reaction. In a certain period of time, the strong acid catalyzes the tert-butoxy carbonyl to remove the tert-butoxy to expose carboxyl, so that the exposed area can be dissolved in alkaline developer. The acid diffusion control agent makes it difficult for the acid generated in the exposed areas to diffuse into the unexposed areas, and the pattern in the unexposed areas is insoluble in the alkaline developer and thus remains, with the overall result that the pattern in the opaque portions of the reticle is transferred to the substrate. The addition of the organometallic salt enhances the adhesion of the conductive traces to the substrate after sintering. The ceramic substrate is used as a base, and the organic gold paste is subjected to printing, leveling, pre-baking, exposure, post-baking, development, drying and sintering to obtain the fine conductive circuit.

The present disclosure will be described with reference to examples of preparation of gold t-butoxycarbonyl-containing resin acid, examples of preparation of organic gold slurry, and test examples, but the present application is not limited thereto. In the examples described below, the chemical reagents used were all chemically 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, a thermometer and a reflux condenser, (8.89 g,0.0625 mol) of t-butyl methacrylate and (29.67 g,0.1875 mol) of thiopyranylmethyl 2-acrylate were diluted in 200mL of toluene, keeping 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. The copolymer 1#34.5g is obtained by decompression filtration, methanol leaching and drying for 6 hours at 50 ℃ in a vacuum drying oven, and the weight average molecular weight is 13996 and the molecular weight distribution is 2.5 by gel permeation chromatography characterization.

(3) Ammonium tetrachloroaurate (37.49 g,0.105 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 0.1 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℃43.2g of gold resinate powder containing carboxyl groups was obtained, designated gold resinate # 1.

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, (10.66 g,0.075 mol) of t-butyl methacrylate and (27.69 g,0.175 mol) of thiopyranyl methyl 2-methyl acrylate were diluted in 200mL of toluene, maintaining 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. The copolymer 2#34.7g is obtained by decompression filtration, methanol leaching and drying for 6 hours at 50 ℃ in a vacuum drying oven, and the weight average molecular weight is 20118 and the molecular weight distribution is 2.6 by gel permeation chromatography characterization.

(3) Ammonium tetrachloroaurate (37.49 g,0.105 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 (21.92 g, sulfur-containing 0.1 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. 44.6g of carboxyl group-containing gold resinate powder, designated gold resinate # 2, was obtained after drying at 40 ℃.

The gold content of the gold resinate 2# was calculated to be 37.7wt% 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, a thermometer and a reflux condenser, (28.44 g,0.20 mol) of t-butyl methacrylate and (47.47 g,0.30 mol) of thiopyranyl methyl 2-methyl acrylate were diluted in 400mL of toluene, keeping 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 in a vacuum drying oven at 50deg.C for 6h to obtain copolymer 3# 68.3g, which has a weight average molecular weight of 23670 and a molecular weight distribution of 2.8 as characterized by gel permeation chromatography.

(3) Ammonium tetrachloroaurate (37.49 g,0.105 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 ℃. The copolymer 3# was weighed (25.3 g, sulfur-containing 0.1 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 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℃48.8g of gold resinate powder containing carboxyl groups was obtained, designated gold resinate 3#.

The gold content of the gold resinate 3# was calculated to be 35.4wt% after sintering at 600 ℃.

Examples 4 to 9: preparation of organic gold slurry 1# -6# -

According to the formulation of Table 1, gold resinate, photoacid generator, sensitizer, acid diffusion control agent and organic metal salt prepared in examples 1 to 3 were dissolved in an organic solvent, and sufficiently and uniformly stirred using a gravity stirrer to obtain a positive-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:

PAG1:4,4' -Dixylyl trifluoro-iodonium mesylate

PAG2: diphenyl- (4-phenylthio) phenylsulfonium hexafluoroantimonate

ITX: 2-isopropyl thioxanthone

Rh: dicarbonyl (pentamethylcyclopentadienyl) rhodium

Pd: palladium pivalate

Base1: trimethyl sulfonium hydroxide salt

Base2: tetrabutylammonium hydroxide

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 baked at 120 ℃ for 120 seconds and then 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 embodiments of the application not disclosed herein, the inventors have found that when the molar ratio of t-butyl methacrylate to thiopyranylmethyl 2-acrylate is below 20:80, the prepared organic gold paste prepared from the gold resinate is difficult to develop in the photoetching process, the conductive line is enlarged, and short circuits occur in partial areas. When the molar ratio of t-butyl methacrylate to thiopyranylmethyl 2-acrylate is higher than 50: at 50, the organogold paste is developed excessively during photolithography, even in the presence of an acid diffusion inhibitor, resulting in development of a portion of the unexposed area, resulting in a larger spacing between the conductive traces and a narrowing of the conductive traces. The inventors have also found that during the preparation of gold resinates, if the molar ratio of gold to sulphur is below 1:1 will result in the gold resinate leaving a cyclic thioether group. In this case, since the acid generated by the photoacid generator catalyzes the elimination of t-butoxy, it also causes the ring-opening polymerization of cyclic thioether, and further causes a crosslinking reaction in the exposed region, which results in the inability of developing the exposed region in the subsequent process, and it is difficult to achieve the purpose of positive lithography for producing fine patterns of the present application. When the combination of the t-butoxycarbonyl group-containing gold resinate, photoacid generator, sensitizer, acid diffusion control agent, organometallic salt and organic solvent is out of the range defined by the present application, it is not only difficult to obtain an organometallic paste suitable for printing viscosity, but also it is easy to cause the fine conductive line after lithography to be not dense and to have a reduced resolution.

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 gold resinate containing t-butoxycarbonyl group is characterized in that the chemical formula is shown as (iii):

wherein n is ₁ 、n ₂ The sum of (2) is an integer of 50 to 300, n ₁ And n ₂ The ratio range of (2): 8-5: 5.

2. a process for the preparation of gold resinate containing t-butoxycarbonyl group as defined in 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 tert-butyl methacrylate and thiopyranylmethyl 2-methyl acrylate, the chemical formula of which is shown as (ii): dissolving tert-butyl methacrylate and (i) obtained in the step 1 in toluene, dropwise adding toluene solution of azo-diisobutyl, 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 、n ₂ The sum of (2) is an integer of 50 to 300, n ₁ And n ₂ The ratio range of (2) is 20: 80-50: 50;

step 3: preparing gold resinate, wherein the chemical formula 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 The sum of (2) is an integer of 50 to 300, n ₁ And n ₂ The ratio range of (2): 8-5: 5.

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 t-butyl methacrylate to thiopyranylmethyl 2-methyl acrylate was 20: 80-50: 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 mole ratio of sulfur to gold is 1, calculated as atoms: 1 to 1:1.05, 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 positive-working lithographic organogold paste characterized by comprising, in parts by mass: 35 to 60 parts of gold resinate according to claim 1 or gold resinate containing tert-butoxycarbonyl group according to any one of the preparation methods of claims 2 to 4, 1 to 5 parts of photoacid generator, 0.1 to 0.5 part of sensitizer, 0.05 to 0.1 part of acid diffusion inhibitor, 30 to 60 parts of organic solvent and 1 to 4 parts of organic metal salt.

6. The positive working photoresist slurry according to claim 5,

the photoacid generator is at least one selected from iodonium salt derivatives, sulfonium salt photoacid generators or oxime sulfonate photoacid generators;

the acid diffusion inhibitor is at least one selected from trimethyl sulfonium hydroxide, tetrabutylammonium hydroxide or 2-phenylbenzimidazole;

the sensitizer is selected from at least one of 2-ethylanthraquinone, N-ethylcarbazole or 2-isopropylthioxanthone;

the organic solvent is selected from at least one of terpineol, turpentine, diethylene glycol butyl ether or dipropylene glycol monobutyl ether;

the organometallic salt is selected from palladium octoate and/or rhodium dicarbonyl (pentamethylcyclopentadienyl).

7. A method for preparing a positive photo-etching organic gold slurry, comprising the following steps: according to the parts by weight, 35 to 60 parts of gold resinate according to claim 1 or gold resinate containing tert-butoxycarbonyl according to any one of the preparation methods according to claims 2 to 4, 1 to 5 parts of photoacid generator, 0.1 to 0.5 part of sensitizer, 0.05 to 0.1 part of acid diffusion inhibitor and 1 to 4 parts of organic metal salt are fully dissolved in 30 to 60 parts of organic solvent and are further uniformly mixed to obtain positive photoetching organic gold slurry.

8. A conductive circuit, wherein the conductive circuit is prepared from the positive photo-etching organic gold slurry according to claim 5 or 6 or the positive photo-etching organic gold slurry according to any one of the preparation methods according to claim 7 through printing, leveling, pre-baking, exposure, post-baking, developing, drying and sintering.