CN115070259A - Novel environment-friendly lead-free soldering paste of superfine soldering tin powder - Google Patents

Novel environment-friendly lead-free soldering paste of superfine soldering tin powder Download PDF

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Publication number
CN115070259A
CN115070259A CN202210837756.6A CN202210837756A CN115070259A CN 115070259 A CN115070259 A CN 115070259A CN 202210837756 A CN202210837756 A CN 202210837756A CN 115070259 A CN115070259 A CN 115070259A
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CN
China
Prior art keywords
powder
resin
acid
solder powder
mass
Prior art date
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Pending
Application number
CN202210837756.6A
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Chinese (zh)
Inventor
刘玉洁
刘家党
黄家强
余海涛
肖东明
卢克胜
肖大为
肖涵飞
肖健
肖雪
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Shenzhen Tong Fang Electronic New Material Co ltd
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Shenzhen Tong Fang Electronic New Material Co ltd
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Priority to CN202210837756.6A priority Critical patent/CN115070259A/en
Publication of CN115070259A publication Critical patent/CN115070259A/en
Pending legal-status Critical Current

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Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B23MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23KSOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/36Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest
    • B23K35/3601Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest with inorganic compounds as principal constituents
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B23MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23KSOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24Selection of soldering or welding materials proper
    • B23K35/26Selection of soldering or welding materials proper with the principal constituent melting at less than 400 degrees C
    • B23K35/264Bi as the principal constituent
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B23MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23KSOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24Selection of soldering or welding materials proper
    • B23K35/30Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
    • B23K35/3006Ag as the principal constituent
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B23MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23KSOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24Selection of soldering or welding materials proper
    • B23K35/30Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
    • B23K35/302Cu as the principal constituent
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B23MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23KSOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24Selection of soldering or welding materials proper
    • B23K35/30Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
    • B23K35/3033Ni as the principal constituent

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Electric Connection Of Electric Components To Printed Circuits (AREA)

Abstract

The invention provides novel environment-friendly lead-free solder paste of superfine solder powder, and relates to the technical field of household kitchens. The novel environment-friendly lead-free solder paste of the superfine solder powder comprises 88-92% of solder powder and the balance of soldering flux, wherein the soldering flux comprises an organic solvent, an active agent, resin, a thixotropic agent and a corrosion inhibitor, the solder powder is subsphaeroidal alloy powder with the granularity of 30-40 mu m, and the solder powder comprises 95-98% of Sn, 1-2% of Cu, 0.1-3% of Ag, 0.1-1% of Bi and 0.01-1% of Ni, and the balance of a surface treatment agent. The surface treatment agent is added to improve the wettability and the surface oxidation resistance of the soldering tin, and the mass ratio of 8: 1: the hydrogenated rosin glyceride, the limonene resin and the dehydrated malic acid resin of the formula 1 can improve the toughness, the oxidation resistance and the thermal stability of the resin, can increase the adhesion of tin paste, and have the functions of protecting and preventing PCB from being oxidized again after welding.

Description

Novel environment-friendly lead-free soldering paste of superfine soldering tin powder
Technical Field
The invention relates to the technical field of welding materials, in particular to novel environment-friendly lead-free solder paste of superfine solder powder.
Background
The soldering paste is a new type of soldering material produced along with SMT, and is a paste mixture formed by mixing soldering tin powder, soldering flux and other surfactants, thixotropic agents, etc. it is mainly used for soldering electronic components of PCB surface resistance, capacitance, IC, etc. in SMT industry, in which the grain form of soldering tin powder, the mass ratio of soldering tin powder and soldering flux and the oxidation degree of soldering tin powder are all the important factors for determining soldering quality
The existing lead-free solder paste uses Cu or Ag with good conductivity to replace Pb of the traditional lead-containing solder paste, the cost is increased along with the environmental protection, the scaling powder of the solder paste usually adopts natural rosin as base resin, but the natural rosin has the problems of easy oxidation, poor thermal stability, brittle texture, easy crack formation, easy superfine development of solder powder, easy oxidation of fine particles, low final reliability of the solder paste, poor stability of a welding point and the like.
Disclosure of Invention
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a novel environment-friendly lead-free soldering paste of superfine soldering powder, which solves the problems that natural rosin is easy to oxidize, poor in thermal stability, crisp in texture and easy to form cracks, and fine particles are easy to oxidize along with the superfine development of the soldering powder, so that the final reliability of the soldering paste is low and the stability of a welding point is poor.
(II) technical scheme
In order to achieve the purpose, the invention is realized by the following technical scheme: the novel environment-friendly lead-free solder paste of the superfine solder powder comprises 88-92% of the total mass of the solder paste and the balance of soldering flux, wherein the soldering flux comprises an organic solvent, an active agent, resin, a thixotropic agent and a corrosion inhibitor.
Preferably, the solder powder adopts near-spherical alloy powder with the grain size of 30-40 μm.
Preferably, the solder powder consists of 95 to 98 percent of Sn, 1 to 2 percent of Cu, 0.1 to 3 percent of Ag, 0.1 to 1 percent of Bi and 0.01 to 1 percent of Ni by mass, and the balance of surface treating agent.
Preferably, the surface treatment agent is formed by mixing 60% of dodecyl phosphate monoester, 20% of quaternary ammonium salt and 20% of polyethylene glycol by mass, and the content of the surface treatment agent is 0.1% -0.5% of the mass of the soldering tin powder.
Preferably, the organic solvent is a mixture of more than two of diethylene glycol dimethyl ether, diethylene glycol diethyl ether, ethylene glycol monobutyl ether, undecanol and dodecanol, and the content of the organic solvent is 40% -55% of the mass of the soldering flux.
Preferably, the active agent is one or a mixture of more of succinic acid, adipic acid, glutaric acid, azelaic acid, sebacic acid, tartaric acid, salicylic acid, phthalic acid and terephthalic acid, and the content of the active agent is 1% -3% of the mass of the soldering flux.
Preferably, the resin is selected from one or more of hydrogenated rosin glyceride, pentaerythritol rosin ester, modified rosin resin, limonene resin, malic acid anhydride resin and alkyd resin, and the content of the resin is 35% -40% of the mass of the soldering flux.
Preferably, the thixotropic agent is one or more of hydrogenated castor oil, hexadecanoic acid amide, fatty acid monoglyceride and fatty acid triglyceride, and the content of the thixotropic agent is 1-5% of the mass of the soldering flux.
Preferably, the corrosion inhibitor is one or more of thiobenzothiazole, benzotriazole and sulfonated lignin, and the content of the corrosion inhibitor is 0.1% -0.9% of the soldering flux.
(III) advantageous effects
The invention provides an environment-friendly lead-free solder paste of novel superfine solder powder. The method has the following beneficial effects:
1. according to the invention, the surface treatment agent formed by mixing the dodecyl phosphate monoester, the quaternary ammonium salt and the polyethylene glycol is added into the solder powder, when the dodecyl phosphate monoester and the quaternary ammonium salt are dispersed in the polyethylene glycol, a protective film can be formed on the surface of the superfine solder powder, the oxidation speed of the solder powder can be slowed down, and meanwhile, the traditional rosin is replaced by selecting the mixture of hydrogenated rosin glycerol ester, limonene resin and dehydrated malic acid resin, so that the toughness, oxidation resistance and thermal stability of the resin can be improved, and the reliability of the solder paste is improved.
2. According to the invention, proper Bi and Ni are added to replace Cu and Ag metal materials, so that the environment is ensured, the contents of Cu and Ag are reduced, the production cost in actual production can be reduced, and meanwhile, Cu, Ag, Bi and Ni are adopted as main alloy components of the soldering tin powder, the primary crystal temperature of the soldering tin powder can be lower than 220 ℃, and the elongation, the shear strength and the tensile strength of the soldering tin paste can be increased.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The first embodiment is as follows:
the embodiment of the invention provides a novel environment-friendly lead-free solder paste of superfine solder powder, which comprises 88-92% of solder powder and the balance of soldering flux, wherein the soldering flux comprises an organic solvent, an active agent, resin, a thixotropic agent and a corrosion inhibitor.
The solder powder is nearly spherical alloy powder with the granularity of 30-40 mu m, and in order to not influence the printing, spot injection and welding effects of the solder paste, the solder powder is specifically selected from solder powder with the granularity of 35 mu m accounting for 60 percent by weight of the solder powder, solder powder with the granularity of 30-35 mu m accounting for 20 percent by weight of the solder powder, and solder powder with the granularity of 35-40 mu m accounting for 20 percent by weight of the solder powder.
The solder powder consists of 95-98% of Sn, 1-2% of Cu, 0.1-3% of Ag, 0.1-1% of Bi and 0.01-1% of Ni by mass, and the balance of a surface treating agent, wherein Pb in the traditional solder powder is replaced by Cu and Ag, so that the pollution of Pb to the environment after the waste electrical components are corroded by acid rain can be prevented, 1% of Cu and 3% of Ag are specifically selected, the solder powder has high tensile strength and good conductive performance, but the cost is high, metal elements of the solder powder are compensated by Bi and Ni, the content of Ag can be properly reduced, and the cost is reduced.
The surface treating agent is formed by mixing 60% of dodecyl phosphate monoester, 20% of quaternary ammonium salt and 20% of polyethylene glycol by mass, the content of the surface treating agent is 0.1-0.5% of the mass of the soldering tin powder, and the solder wettability and the surface oxidation resistance can be improved.
The organic solvent is a mixture of more than two of diethylene glycol dimethyl ether, diethylene glycol diethyl ether, ethylene glycol monobutyl ether, undecanol and dodecanol, the content of the organic solvent is 40-55% of the mass of the soldering flux, and the mass ratio is 4: 4: the diethylene glycol dimethyl ether, the diethylene glycol diethyl ether and the ethylene glycol monobutyl ether of the 3 have low melting points, low melting conditions and low energy consumption, but have slow crystallization speed, and are not beneficial to the welding of multiple welding spots and large workload.
The active agent is one or a mixture of more of succinic acid, adipic acid, glutaric acid, azelaic acid, sebacic acid, tartaric acid, salicylic acid, phthalic acid and terephthalic acid, the content of the active agent is 1-3% of the mass of the soldering flux, the effect of removing oxidation substances on the surface layer of a PCB copper film pad and the welding part of a part can be achieved, and the effect of reducing the surface tension of tin can be achieved.
The resin is composed of one or more of hydrogenated rosin glyceride, pentaerythritol rosin ester, modified rosin resin, limonene resin, malic acid anhydride resin and alkyd resin, the content of the resin is 35% -40% of the mass of the soldering flux, and the resin is prepared by mixing the following components in percentage by mass: 1: the hydrogenated rosin glyceride, the limonene resin and the dehydrated malic acid resin of the formula 1 can improve the toughness, the oxidation resistance and the thermal stability of the resin, can increase the adhesion of tin paste, and have the functions of protecting and preventing PCB from being oxidized again after welding.
The thixotropic agent is selected from one or more of hydrogenated castor oil, hexadecanoic acid amide, fatty acid monoglyceride and fatty acid triglyceride, the content of the thixotropic agent is 1-5% of the mass of the soldering flux, and the thixotropic agent plays a role in preventing trailing, adhesion and other phenomena in printing by adjusting the viscosity and the printing performance of the solder paste.
The corrosion inhibitor is selected from one or more of sulfenyl benzothiazole, benzotriazole and sulfonated lignin, the content of the corrosion inhibitor is 0.1-0.9% of that of the soldering flux, the corrosion inhibitor can slow down the corrosion speed of the soldering point, and the durability and the stability of the soldering point are improved.
Example two:
the embodiment of the invention provides a novel environment-friendly lead-free solder paste of superfine solder powder, which comprises 88-92% of solder powder and the balance of soldering flux, wherein the soldering flux comprises an organic solvent, an active agent, resin, a thixotropic agent and a corrosion inhibitor.
The solder powder is nearly spherical alloy powder with the granularity of 30-40 mu m, and in order to not influence the printing, spot injection and welding effects of the solder paste, the solder powder is specifically selected from solder powder with the granularity of 35 mu m accounting for 60 percent by weight of the solder powder, solder powder with the granularity of 30-35 mu m accounting for 20 percent by weight of the solder powder, and solder powder with the granularity of 35-40 mu m accounting for 20 percent by weight of the solder powder.
The solder powder consists of 95-98% of Sn, 1-2% of Cu, 0.1-3% of Ag, 0.1-1% of Bi, 0.01-1% of Ni and the balance of a surface treating agent by mass, Pb in the traditional solder powder is replaced by the Cu and the Ag, the pollution of Pb to the environment after the waste electrical components are corroded by acid rain can be prevented, and the cost can be controlled while the tensile strength and the good conductive performance of welding are ensured by specifically selecting the 2% of Cu and the 1% of Ag.
The surface treating agent is formed by mixing 60% of dodecyl phosphate monoester, 20% of quaternary ammonium salt and 20% of polyethylene glycol by mass, the content of the surface treating agent is 0.1-0.5% of the mass of the soldering tin powder, and the solder wettability and the surface oxidation resistance can be improved.
The organic solvent is a mixture of more than two of diethylene glycol dimethyl ether, diethylene glycol diethyl ether, ethylene glycol monobutyl ether, undecanol and dodecanol, the content of the organic solvent is 40% -55% of the mass of the soldering flux, and the diethylene glycol dimethyl ether and the undecanol are selected in a mass ratio of 3: 2, so that the soldering flux can be rapidly melted, the crystallization speed can be high, the overall soldering time is short, and the soldering efficiency is high.
The active agent is one or a mixture of more of succinic acid, adipic acid, glutaric acid, azelaic acid, sebacic acid, tartaric acid, salicylic acid, phthalic acid and terephthalic acid, and the content of the active agent is 1-3% of the mass of the soldering flux.
The resin is composed of one or more of hydrogenated rosin glyceride, pentaerythritol rosin ester, modified rosin resin, limonene resin, malic acid anhydride resin and alkyd resin, the content of the resin is 35% -40% of the mass of the soldering flux, and the resin is prepared by mixing the following components in percentage by mass: 1: the hydrogenated rosin glyceride, the limonene resin and the dehydrated malic acid resin of the formula 1 can improve the toughness, the oxidation resistance and the thermal stability of the resin, can increase the adhesion of tin paste, and have the functions of protecting and preventing PCB from being oxidized again after welding.
The thixotropic agent is one or more of hydrogenated castor oil, hexadecanoic acid amide, fatty acid monoglyceride and fatty acid triglyceride, the content of the thixotropic agent is 1-5% of the mass of the soldering flux, and the thixotropic agent plays a role in preventing trailing, adhesion and other phenomena in printing by adjusting the viscosity and the printing performance of the soldering paste.
The corrosion inhibitor is selected from one or more of sulfenyl benzothiazole, benzotriazole and sulfonated lignin, the content of the corrosion inhibitor is 0.1-0.9% of that of the soldering flux, the corrosion inhibitor can slow down the corrosion speed of the soldering point, and the durability and the stability of the soldering point are improved.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.

Claims (9)

1. The utility model provides a novel unleaded solder paste of environmental protection of superfine solder powder, includes solder powder and scaling powder, its characterized in that: the mass of the soldering tin powder accounts for 88-92% of the total mass of the soldering tin paste, and the balance is soldering flux, wherein the soldering flux comprises an organic solvent, an active agent, resin, a thixotropic agent and a corrosion inhibitor.
2. The environment-friendly lead-free solder paste of the novel ultrafine solder powder as claimed in claim 1, wherein: the solder powder adopts near-spherical alloy powder with the granularity of 30-40 mu m.
3. The environment-friendly lead-free solder paste of the novel ultrafine solder powder as claimed in claim 1, wherein: the soldering tin powder consists of 95-98% of Sn, 1-2% of Cu, 0.1-3% of Ag, 0.1-1% of Bi and 0.01-1% of Ni by mass, and the balance of a surface treating agent.
4. The environment-friendly lead-free solder paste of the novel ultrafine solder powder as claimed in claim 2, wherein: the surface treating agent is formed by mixing 60% of dodecyl phosphate monoester, 20% of quaternary ammonium salt and 20% of polyethylene glycol by mass, and the content of the surface treating agent is 0.1% -0.5% of the mass of the soldering tin powder.
5. The environment-friendly lead-free solder paste of the novel ultrafine solder powder as claimed in claim 1, wherein: the organic solvent is a mixture of more than two of diethylene glycol dimethyl ether, diethylene glycol diethyl ether, ethylene glycol monobutyl ether, undecanol and dodecanol, and the content of the organic solvent is 40-55% of the mass of the soldering flux.
6. The environment-friendly lead-free solder paste of the novel ultrafine solder powder as claimed in claim 1, wherein: the active agent is one or a mixture of more of succinic acid, adipic acid, glutaric acid, azelaic acid, sebacic acid, tartaric acid, salicylic acid, phthalic acid and terephthalic acid, and the content of the active agent is 1-3% of the mass of the soldering flux.
7. The environment-friendly lead-free solder paste of the novel ultrafine solder powder as claimed in claim 1, wherein: the resin is composed of one or more of hydrogenated rosin glyceride, pentaerythritol rosin ester, modified rosin resin, limonene resin, malic acid anhydride resin and alkyd resin, and the content of the resin is 35% -40% of the mass of the soldering flux.
8. The environment-friendly lead-free solder paste of the novel ultrafine solder powder as claimed in claim 1, characterized in that: the thixotropic agent is selected from one or more of hydrogenated castor oil, hexadecanoic acid amide, fatty acid monoglyceride and fatty acid triglyceride, and the content of the thixotropic agent is 1-5% of the mass of the soldering flux.
9. The novel environment-friendly lead-free solder paste of ultrafine solder powder as claimed in claim 1, wherein the corrosion inhibitor is selected from one or more of thiobenzothiazole, benzotriazole and sulfonated lignin, and the content of the corrosion inhibitor is 0.1-0.9% of the soldering flux.
CN202210837756.6A 2022-07-15 2022-07-15 Novel environment-friendly lead-free soldering paste of superfine soldering tin powder Pending CN115070259A (en)

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CN115673598A (en) * 2022-10-29 2023-02-03 江苏三沃电子科技有限公司 Preparation process of soldering paste
CN115673598B (en) * 2022-10-29 2023-11-21 江苏三沃电子科技有限公司 Preparation process of soldering paste

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