阅读说明：本技术 一种抗氧化低腐蚀的低温固化导电油墨 (Low-temperature curing conductive ink with oxidation resistance and low corrosion resistance ) 是由 何伟雄 黄大凯 肖海明 吴依阳 于 2019-10-23 设计创作，主要内容包括：本发明公开了一种抗氧化低腐蚀可以低温固化的导电油墨,其配方中各个组分的重量份数为,树脂中间体30-75份,溶剂4-25份,抗氧化剂0.5-5份,银粉10-50份,助剂为0.5-5份。树脂为羟基或羧基改性的三元氯醋树脂,分子量在15000至65000之间,K在35至60之间。溶剂选自二乙二醇丁醚醋酸酯、二乙二醇丁醚、乙二醇、乙二醇丁醚醋酸酯、乙二醇丁醚、1,4-丁二醇、三乙二醇丁醚、三丙二醇、一缩二乙二醇、三丙二醇丁醚、3-甲氧基-3-甲基-1-丁醇、二丙二醇甲醚中一种或多种,树脂中间体为溶剂稀释过后的树脂。本发明有效改变导电油墨漆膜表面逐步发黄的现象,并且还能防止导电油墨对塑料薄膜诸如PVC、PC、ABS、PMMA等基材的“咬底”缺陷,有效提高产品质量。(The invention discloses an antioxidant low-corrosion conductive ink capable of being cured at low temperature, which comprises, by weight, 30-75 parts of a resin intermediate, 4-25 parts of a solvent, 0.5-5 parts of an antioxidant, 10-50 parts of silver powder and 0.5-5 parts of an auxiliary agent. The resin is hydroxyl or carboxyl modified ternary vinyl chloride-vinyl acetate copolymer resin with molecular weight of 15000-65000 and K of 35-60. The solvent is one or more selected from diethylene glycol butyl ether acetate, diethylene glycol butyl ether, ethylene glycol butyl ether acetate, ethylene glycol butyl ether, 1, 4-butanediol, triethylene glycol butyl ether, tripropylene glycol, diethylene glycol, tripropylene glycol butyl ether, 3-methoxy-3-methyl-1-butanol and dipropylene glycol methyl ether, and the resin intermediate is resin after solvent dilution. The invention effectively changes the gradual yellowing phenomenon of the surface of the conductive ink paint film, can also prevent the bottom biting defect of the conductive ink on plastic films such as PVC, PC, ABS, PMMA and other substrates, and effectively improves the product quality.)

1. The low-temperature curing conductive ink with the oxidation resistance and the low corrosion resistance is characterized by comprising the following raw materials in parts by weight: 30-75 parts of resin intermediate, 4-25 parts of solvent, 0.5-5 parts of antioxidant, 10-50 parts of silver powder and 0.5-5 parts of auxiliary agent, wherein the resin intermediate consists of 60-95% of resin and 5-40% of solvent, and the solvent is low-corrosion solvent.

2. The low temperature curable conductive ink according to claim 1, wherein the resin has an average degree of polymerization of 35 to 60.

3. The low-temperature-curable conductive ink according to claim 2, wherein the resin is one or two selected from hydroxyl-modified trichloro-vinyl acetate terpolymer and carboxyl-modified trichloro-vinyl acetate terpolymer, and the molecular weight of the resin is 15000 to 65000.

4. The low temperature curable conductive ink according to claim 1, wherein the solvent is selected from one or more of diethylene glycol butyl ether acetate, diethylene glycol butyl ether, ethylene glycol butyl ether acetate, ethylene glycol butyl ether, 1, 4-butanediol, triethylene glycol butyl ether, tripropylene glycol, diethylene glycol, tripropylene glycol butyl ether, 3-methoxy-3-methyl-1-butanol, and dipropylene glycol methyl ether.

5. The low-temperature curable conductive ink according to claim 1, wherein the antioxidant is prepared from a thermal oxidant resistant, ultraviolet absorber in a ratio of (0.1-10): (0.1-10) by weight;

the heat-resistant oxidant is selected from one or more of pentaerythritol tetrakis (beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate), tris [2, 4-di-tert-butylphenyl ] phosphite, N '-bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine, N-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, N' -bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl ] hydrazine, thiodiethylbis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], and didodecyl thiodipropionate;

the ultraviolet absorbent is selected from one or more of 2- (2' -hydroxy-3 ',5' -di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2' -hydroxy-5 ' -tert-octylphenyl) benzotriazole, 2-hydroxy-4-n-octyloxybenzophenone, 2- (2' -hydroxy-5 ' -methylphenyl) benzotriazole, 2' - (2' -hydroxy-3 ' -tert-butyl-5 ' -methylphenyl) -5-chlorobenzotriazole, and bis (2,2,6, 6-tetramethyl-4-piperidyl) sebacate.

6. The low-temperature curing conductive ink according to claim 1, wherein the silver powder is an oxidation-resistant micron-sized plate-like silver powder, and the average particle size of the silver powder is 2.0 to 12.0 μm.

7. The low-temperature-curable conductive ink according to claim 6, wherein the silver powder has a bulk density of 0.2 to 0.9g/cm³The tap density is 1.0 to 4.0g/cm³。

8. The low-temperature-curing conductive ink as claimed in claim 1, wherein the auxiliary agent is one or more selected from a defoaming agent, an adhesion promoter, a dispersing agent and a leveling agent.

9. A method of making the conductive ink of any one of claims 1-8, comprising the steps of:

step 1: mixing the resin intermediate, the solvent, the antioxidant, the silver powder and the auxiliary agent according to a set proportioning relation, and preheating to 30-45 ℃;

step 2: placing the mixture obtained in the step 1 in a high-speed shearing dispersion machine, uniformly dispersing under the condition of 500-1200r/min, and fully grinding on a three-roll grinder until the particle size is less than 7 mu m;

and step 3: filtering with 150-mesh and 250-mesh filter screen, and packaging to obtain the final product.

10. The method for preparing the conductive ink as claimed in claim 9, wherein the resin intermediate is preheated to 30-45 ℃ before mixing in step 1, and is uniformly dispersed in a high-speed shear disperser at a speed of 500-1200 r/min.

Technical Field

The invention relates to a conductive ink, in particular to an antioxidant low-corrosion low-temperature curing conductive ink.

Background

The low-temperature cured conductive ink is widely applied to the fields of electronic components such as display screens, membrane switches, flexible circuits and the like, and makes the lightening, thinning and intelligentization of electronic products possible. However, with the development of electronic products such as foldable mobile phones, curved televisions and the like which are widely popularized in the market in recent years, higher requirements are placed on the performance of flexible screens and flexible circuits, and further higher performance requirements are placed on conductive ink which plays a key role in such electronic components.

The traditional conductive ink or conductive silver paste is usually printed on the surface of aging-resistant and corrosion-resistant substrates such as PET (polyethylene terephthalate plastic), silicone, PP (polypropylene plastic), PE (polyethylene plastic), PI (polyimide plastic), ITO (indium tin oxide), glass, and the like, so that the raw materials and solvents used by the conductive ink are not harsh, and the conductive ink is sealed by insulating glue or an insulating film after the surface of the substrates is cured, thereby isolating the contact between the ink and air and preventing the cured ink from being oxidized.

However, with the advance of science and technology, in order to realize the flexibility of electronic components, conductive ink needs to be printed on film substrates which are not resistant to solvent corrosion, such as PC (polycarbonate plastic), PVC (polyvinyl chloride plastic), ABS (engineering plastic), PMMA (acrylic plastic), and the like, so that the substrates are easily swelled and deformed by corrosive solvents in the production process, and the conventional conductive ink or conductive silver paste generally needs to use ketone and ester solvents as diluents to adjust the viscosity, so as to facilitate the construction such as printing and coating, and these solvents include cyclohexanone, isophorone, DBE, ethylene glycol diacetate, and the like, which not only has unpleasant odor, but also easily causes the corrosion of the substrates, and the phenomenon of 'bottom biting' occurs. In addition, in order to ensure high flexibility of the electronic element, the insulating glue or the insulating film structure is gradually cancelled, so that the membrane switch or the flexible circuit needs to be exposed in the air, the conductive ink is easily oxidized by the outside air and soaked by sweat of a human body, yellowing and the like are caused, and the service life is shortened.

Disclosure of Invention

The invention provides an antioxidant low-corrosion low-temperature curing conductive ink, which at least solves the problem that the conductive ink in the prior art is easy to corrode plastics.

The invention provides an antioxidant low-corrosion low-temperature curing conductive ink which is prepared from the following raw materials in parts by weight: 30-75 parts of resin intermediate, 4-25 parts of solvent, 0.5-5 parts of antioxidant, 10-50 parts of silver powder and 0.5-5 parts of auxiliary agent, wherein the resin intermediate consists of 60-95% of resin and 5-40% of solvent, and the solvent is low-corrosion solvent.

Further, the average polymerization degree of the resin is 35 to 60.

Still further, the resin is selected from one or two of hydroxyl modified ternary vinyl chloride-vinyl acetate copolymer and carboxyl modified ternary vinyl chloride-vinyl acetate copolymer, and the molecular weight of the resin is between 15000 and 65000.

Further, the solvent is selected from one or more of diethylene glycol butyl ether acetate, diethylene glycol butyl ether, ethylene glycol butyl ether acetate, ethylene glycol butyl ether, 1, 4-butanediol, triethylene glycol butyl ether, tripropylene glycol, diethylene glycol, tripropylene glycol butyl ether, 3-methoxy-3-methyl-1-butanol and dipropylene glycol methyl ether.

Further, the antioxidant is prepared from a heat-resistant oxidant and an ultraviolet absorber according to the ratio of (0.1-10): (0.1-10) by weight;

the heat-resistant oxidant is selected from one or more of pentaerythritol tetrakis (beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate), tris [2, 4-di-tert-butylphenyl ] phosphite, N '-bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine, N-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, N' -bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl ] hydrazine, thiodiethylbis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], and didodecyl thiodipropionate;

the ultraviolet absorbent is selected from one or more of 2- (2' -hydroxy-3 ',5' -di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2' -hydroxy-5 ' -tert-octylphenyl) benzotriazole, 2-hydroxy-4-n-octyloxybenzophenone, 2- (2' -hydroxy-5 ' -methylphenyl) benzotriazole, 2' - (2' -hydroxy-3 ' -tert-butyl-5 ' -methylphenyl) -5-chlorobenzotriazole, and bis (2,2,6, 6-tetramethyl-4-piperidyl) sebacate.

Further, the silver powder is antioxidant micron-sized flaky silver powder, and the average particle size of the silver powder is 2.0-12.0 microns.

Further, the silver powder has a bulk density of 0.2 to 0.9g/cm³The tap density is 1.0 to 4.0g/cm³

Further, the auxiliary agent is selected from one or more of a defoaming agent, an adhesion promoter, a dispersing agent and a leveling agent.

The invention also discloses a preparation method of the conductive ink, which comprises the following steps:

step 1: mixing the resin intermediate, the solvent, the antioxidant, the silver powder and the auxiliary agent according to a set proportioning relation, and preheating to 30-45 ℃;

step 2: placing the mixture obtained in the step 1 in a high-speed shearing dispersion machine, uniformly dispersing under the condition of 500-1200r/min, and fully grinding on a three-roll grinder until the particle size is less than 7 mu m;

and step 3: filtering with 150-mesh and 250-mesh filter screen, and packaging to obtain the final product.

Further, in the step 1, the resin intermediate needs to be preheated to 30-45 ℃ before mixing, and is uniformly dispersed in a high-speed shear disperser according to the conditions of 500-1200 r/min.

Compared with the prior art, the conductive ink disclosed by the invention solves the problem that the conductive ink has higher corrosion capability on substrates such as PC (polycarbonate plastic), PVC (polyvinyl chloride plastic), ABS (engineering plastic), PMMA (acrylic plastic) and the like, ensures that the conductive ink has the advantages of low corrosion, sweat resistance, bending resistance, oxidation resistance and low yellowing while maintaining excellent conductivity.

Detailed Description

In order to make the technical solutions of the present invention better understood by those skilled in the art, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments.