CN114289932B - Halogen-free cleaning-free lead-free soldering tin wire soldering flux and preparation method thereof - Google Patents
Halogen-free cleaning-free lead-free soldering tin wire soldering flux and preparation method thereof Download PDFInfo
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Abstract
A halogen-free no-clean lead-free soldering tin wire soldering flux and a preparation method thereof are disclosed, the soldering flux comprises the following raw materials: 2.0-10.0% of compound organic carboxylic acid, 0.1-1.5% of high-activity covalent iodine activator, 0.5-5.0% of halogen-free activity reinforcing agent, 0.1-1.0% of surfactant, 0.1-1.0% of antioxidant, 0.1-1.0% of corrosion inhibitor, 3.0-8.0% of compound solvent and the balance of compound modified rosin resin. The preparation method comprises the steps of heating, stirring and melting the compound modified rosin resin, adding the compound organic acid and the halogen-free activity reinforcing agent, adding the compound solution in which the high-activity covalent iodine activating agent, the surfactant, the antioxidant and the corrosion inhibitor are dissolved, and finally stirring and dissolving at constant temperature until the components are uniformly mixed to obtain the soldering flux. The halogen-free and cleaning-free soldering flux for the lead-free soldering tin wire has the characteristics of high activity, easy tin feeding in welding, low splashing, low corrosion, small residue, high surface insulation resistance and the like, meets the non-halogenation standard of green environmental protection and welding application, and ensures the reliability of electronic and electric products after welding.
Description
Technical Field
The invention belongs to the technical field of electronic soft soldering materials, and particularly relates to a lead-free soldering tin wire soldering flux and a preparation method thereof.
Background
With the development of society, people have stronger environmental protection consciousness, the research and development and application of the solder wire at home and abroad have taken the way of green environmental protection, and the lead-free soft solder alloy and the halogen-free soldering flux are popular subjects for market development. At present, the solder alloy technology for cored solder wires is relatively mature, mainly comprising Sn-Cu series and Sn-Ag-Cu series, but the soldering flux technology has a plurality of unsolved technical barriers, and for lead-free solders with the same specification, the soldering flux plays a decisive role in the performance of the solder wires.
Halogen includes fluorine (F), chlorine (Cl), bromine (Br), iodine (I), astatine (At), wherein astatine belongs to a radioactive element, and one generally refers to halogen as fluorine, chlorine, bromine, iodine. Halogen-Free english name is Halogen Free, abbreviated as HF, and since Halogen flame retardant compounds (such as PBB, PCB, PBDE, tribromophenol, etc.) applied to electronic parts and materials thereof, product housings, plastics, etc. cannot be recycled, harmful substances are released in the combustion or heating process, pollute the environment, threaten the life health of human beings, thus, countries in the world impose strict restrictions on Halogen, i.e. no halogenation. For halogen-free requirements, different products have different limited standards, and in the technical field of electronic soldering materials, environmental protection halogen-free definition of EU RoHS instruction is as follows: according to the requirements of the regulation IEC 61249-2-21: br < 900ppm, cl < 900ppm, and Br + Cl < 1500ppm, is halogen-free. However, in consideration of the application performances such as the Surface Insulation Resistance (SIR) and the electrochemical migration (ECM) of the flux, the joint enterprise standard IPC J-STD-004B defines the halogen-free no-clean flux from the application end: when halide content is expressed as equivalent percentage of chloride in the solid (non-volatile) components of the flux as halide and the sum of the weight percentages of ionic halides in the flux solids is less than 0.05%, the flux is considered to be a halide-free flux, i.e., F - +Cl - +Br - +I - When the flux is less than 500ppm, the flux is halogen-free cleaning-free flux. The above two kinds are halogen-freeThe definitions are internationally recognized as the most common definition, wherein halogen-free in the former definition means free of halogens, including ionic halides and covalent halides, and is defined from an environmental point of view with only Br and Cl, and without F and I being limited. While halogen-free in the latter definition means that there is no halide ion, only ionic halides are included, while F is limited - 、Cl - 、Br - 、I - Defined from a welding application perspective. The components of the soldering flux only contain covalent iodine compounds, and do not contain any ionic halide or other covalent halides, so that the halogen-free no-clean soldering tin wire soldering flux meets the environmental protection halogen-free requirement of IEC 61249-2-21 and the application halogen-free requirement of IPC J-STD-004B.
A great deal of research work is carried out on the halogen-free soldering flux by a plurality of related enterprises, colleges and universities, research and development institutions and scientific and technical workers at home and abroad. Chinese invention patent CN102248317A discloses a halogen-free lead-free solder wire, which adopts one or a combination of glutaric acid and ethylenediamine as an active agent system of a soldering flux, the mass percentage of the active agent system is 0.02 to 0.04 percent, although no halogen active agent exists in the formula, only a small amount of organic acid is used as the active agent, the activity of the soldering flux is obviously insufficient, and the solder wire product is difficult to realize generalization in the aspect of welding application. Chinese invention patent CN101062536A discloses a halogen-free no-clean soldering flux for lead-free soldering tin, which adopts 1.5 to 3.5 percent of organic acid activator and 2.0 to 5.0 percent of organic amine and derivatives thereof as an activator system of the soldering flux, the organic acid and the organic amine can generate neutralization reaction after being mixed, the generated neutralization product can be decomposed into the organic acid and the organic amine at the soldering temperature, active ingredients are consumed, the soldering activity is influenced, the soldering speed is slowed down, and in addition, the soldering flux containing the organic amine can generate irritant gas and a large amount of dense smoke in the high-temperature soldering process. Chinese patent CN102284809A discloses a halogen-free no-clean soldering flux for a tin wire core, which adopts 0.5 to 5.0% of stannous oxalate and 0.5 to 25.0% of organic acid activator as a soldering flux activator system, however, the stannous oxalate belongs to a metal ion organic compound, and subsequent SIR and ECM performance tests may not reach the standard after welding, and in addition, no corrosion inhibition component is mentioned in the patent document, and the activator component in the soldering flux residue after welding may corrode a welding base material. Chinese patent CN104191108A discloses a halogen-free high-activity low-splashing soldering tin wire soldering flux and a preparation method thereof, wherein 0.08 to 1.5% of high-activity iodized salt, 2.0 to 10% of compound organic dicarboxylic acid, 0.5 to 5.0% of halogen-free activity reinforcing agent and 0.04 to 0.2% of covalent fluorine high-efficiency surfactant are adopted as an active agent system, compound modified rosin is adopted as a film forming agent, high-boiling point alcohols or alcohol ethers such as tetrahydrofurfuryl alcohol, triethylene glycol butyl ether and the like are adopted as solvents, viscosity regulators such as hydrogenated rosin alcohol, pentaerythritol tetrabenzoate and the like are adopted to adjust the viscosity of the soldering flux, the high-activity and low-splashing requirements in the welding application can be met, the environmental-friendly halogen-free requirements of RoHS instructions of European Union are also met, the application halogen-free requirements of IPC J-STD-004B are not met, and in addition, reddish precipitates can appear in the soldering flux preparation process, the fluorine-containing surfactant is generally harmful to the environment, and many fluoride are definitely forbidden to manufacturers. Chinese invention patent CN101049662A discloses a halogen-free soldering flux for lead-free soft solder wire and a preparation method thereof, wherein the formula of the soldering flux consists of 0.2 to 3.0 percent of organic acid activator, 0.2 to 3.0 percent of nonionic surfactant and the balance of rosin, wherein the nonionic surfactant is at least one of dibromobutenediol, dibromoethylbenzene, bromohexadecylpyridine and FSN-100, the bromine content in covalent halogenation exceeds 900ppm, and does not meet the halogen-free standard of European Union RoHS instruction.
In summary, the activator system is the most critical technical breakthrough for the research and development of the flux formula technology for halogen-free and clean-free soldering wires, in order to achieve the technical standard of halogen-free and clean-free soldering wire flux, firstly, only organic acid or organic amine is used as the activator, secondly, the combination of the organic acid, the organic amine and derivatives thereof is used as the activator, the flux prepared by the two schemes may face the performance challenges of weak welding activity and large corrosivity after welding, especially the organic amine activator may generate irritant gas and a large amount of dense smoke in the welding process; the metal ion organic compound is directly introduced into an activator system, so that the activity of the soldering flux can be improved, the halogen-free standard can be met, the subsequent SIR and ECM performance tests may not meet the standards, and in addition, the residual activator component of the soldering flux after welding may cause severe corrosion to a welding base material. Some activator systems introduce ionic iodide or covalent fluoride, which reaches the environmental protection halogen-free standard of European Union RoHS instruction, but does not reach the application halogen-free standard of IPC J-STD-004B. Some activator systems only introduce covalent halide to reach the application halogen-free standard of IPC J-STD-004B, but cannot reach the environmental protection halogen-free standard of European Union RoHS instruction. In the meaning of strict halogen-free, the latter two halogen-free technical schemes are both used for beating halogen-free standard edge-wiping balls, and are not pure halogen-free cleaning-free soldering flux technology.
Disclosure of Invention
The invention aims to solve the defects of the prior art, provides the halogen-free no-clean lead-free soldering tin wire soldering flux which is green and environment-friendly, has high activity, high tin applying speed, easy wetting, low corrosion, low residue and excellent splashing performance in the welding process, and also provides the preparation method of the soldering flux.
The technical scheme adopted by the invention is as follows:
the halogen-free no-clean lead-free soldering tin wire soldering flux comprises the following raw materials in percentage by weight:
2.0 to 10.0 percent of compound organic carboxylic acid
High activity covalent iodine activator 0.1-1.5%
0.5 to 5.0 percent of halogen-free activity reinforcing agent
0.1 to 1.0 percent of surfactant
0.1 to 1.0 percent of antioxidant
0.1 to 1.0 percent of corrosion inhibitor
3.0 to 8.0 percent of compound solvent
Compound modified rosin resin surplus
The compound organic carboxylic acid is a combination of two or more than two of 2-pyridine carboxylic acid, p-hydroxyphenylacetic acid, 2,2-dimethylolpropionic acid, dimethylolbutyric acid, tetradecanoic acid, hexadecanoic acid, methylsuccinic acid, glutaric anhydride, adipic acid, suberic acid, sebacic acid, mixed dibasic acid and malic acid;
the high-activity covalent iodine activator is a high-activity covalent iodine activator A1 sold by Shenzhen Macro industry Limited;
the halogen-free activity reinforcing agent is one or more of ST-200, ST-400 and FR-500 sold by Shenzhen, jin Teng Longindustry Limited;
the surfactant is one or more of oleyl alcohol polyoxyethylene ether, surfynol 104E, dynol 604, surfynol AD01, surfynol DM20 and Surfynol DF 110D;
the antioxidant is one or two of a gasoline engine antioxidant 1010 and an antioxidant BHT;
the corrosion inhibitor is benzotriazole;
the compound solvent is a combination of a low-boiling point solvent and a high-boiling point solvent; the low-boiling-point solvent is one or more of ethylene glycol monomethyl ether, propylene glycol monomethyl ether and propylene glycol diethyl ether, and the high-boiling-point solvent is one or more of tetrahydrofurfuryl alcohol, ethanolamine, propylene glycol propyl ether, propylene glycol butyl ether, diethylene glycol methyl ether, tripropylene glycol butyl ether, diethylene glycol hexyl ether and dipropylene glycol butyl ether;
the compound modified rosin resin is a combination of two or more than two of refined hydrogenated rosin, eastman perhydrogenated rosin AX-E, perhydrogenated rosin RHR-3130HS, refined hydrogenated acrylic acid modified rosin, taiwan 685 leadless rosin and water white rosin.
The invention relates to a preparation method of a halogen-free no-clean lead-free soldering tin wire soldering flux, which comprises the following steps:
(1) Adding the compound modified rosin resin into a reactor, heating, stirring and melting completely;
(2) Adding compound organic carboxylic acid and halogen-free activity reinforcing agent into the compound modified rosin resin melted in the step (1), heating, stirring at constant temperature and melting completely to obtain compound material;
(3) Dissolving a high-activity covalent iodine activator, a surfactant, an antioxidant and a corrosion inhibitor in a compound solvent to obtain a compound solution;
(4) And (3) adding the compound solution prepared in the step (3) into the compound material prepared in the step (2), heating and continuously stirring at constant temperature until the compound material and the compound solution are uniformly mixed to obtain the halogen-free and cleaning-free lead-free soldering tin wire soldering flux.
Further, the heating temperature of the compound modified rosin resin in the step (1) is 150 +/-10 ℃; the heating constant temperature of the compound material prepared in the step (2) is 150 +/-10 ℃; and (4) the heating constant temperature of the halogen-free no-clean lead-free solder wire soldering flux prepared in the step (4) is 150 +/-10 ℃.
The halogen-free no-clean lead-free soldering tin wire soldering flux has the following advantages:
(1) The soldering flux only contains covalent iodine compounds, does not contain any ionic halide or other covalent halides, meets the environment-friendly halogen-free requirements of ' Br less than 900ppm, cl less than 900ppm and Br + Cl less than 1500ppm ' of the regulation IEC 61249-2-21 of RoHS directive of European Union, and also meets the ' F J-STD-004B standard of the United enterprises - +Cl - +Br - +I - < 500ppm "application halogen free requirements. Therefore, the soldering flux disclosed by the invention realizes non-halogenation in the aspects of environmental protection and application, belongs to a halogen-free and cleaning-free soldering flux, and is harmless to human health and environment.
(2) The novel covalent iodine activator A1 produced by Shenzhen Macro industry Limited has a molecule which contains covalent iodine and also has a monobasic organic carboxylic acid functional group, the activity of the covalent iodine activator is far superior to that of conventional organic carboxylic acid and is close to that of halogen salt (such as cyclohexylamine hydrobromide and the like), so that the covalent iodine activator has excellent welding activity, and the covalent iodine activator is a covalent compound containing a branched chain, so that the covalent iodine activator has a certain inhibition effect on splashing. The covalent iodine activator is chemically stable under normal conditions and does not corrode welded metal substrates, but the carboxylic acid functional group in the activator molecule ionizes H during high temperature welding + And the covalent bond of the moiety "-I" is broken at high temperature to convert intoFree I － ，H + And I － The activity of the solder is released at the same time, so that the metal oxide on the surface of the welding base material can be effectively removed, the surface tension is reduced, the solder and the welded base material are mutually soaked, and the soldering assisting performance is enhanced. In addition, the activator molecules are mostly oxidatively decomposed during high temperature welding, and thus the residue is relatively low. The novel covalent iodine activator used by the invention not only makes up the defect of low activity of other halogen-free salt or organic carboxylic acid activators, but also has the advantage of high activity close to that of halogen salt, and can be used as an activator component in the formula of various soldering fluxes to prepare various high-activity halogen-free cleaning-free soldering fluxes. In addition, the activator system of the invention is also added with compound organic carboxylic acid, including monobasic organic carboxylic acid, dibasic organic carboxylic acid and tribasic organic carboxylic acid, the physical and chemical properties of the organic carboxylic acid are stable, the smog and smell during welding are conventional, and by compounding two or more organic carboxylic acids, the fluxing effect can be ensured, the active temperature range of the organic carboxylic acid can be enlarged, and the comprehensive performance of the soldering flux can be improved. Therefore, under the matching use of the novel covalent iodine activator and the compound organic carboxylic acid, the soldering flux has high activity and is generally used for soldering tin-plated, copper-plated and other weldments.
(3) The corrosion inhibitor adopted by the invention is benzotriazole, and has excellent corrosion inhibition performance on organic carboxylic acid. After the welding operation is finished, the benzotriazole can effectively relieve the corrosion of residues of the high-activity covalent iodine activator, the compound organic carboxylic acid and the like adopted in the invention to the weldment. The use of the corrosion inhibitor does not affect the activity of the organic carboxylic acid activator in the soldering flux, and can solve the problem that the residual organic carboxylic acid causes corrosion to the weldment, which is also the key point that organic carboxylic acid is ignored as an activator system in many halogen-free no-clean soldering flux formulas in the prior art.
(4) The invention adopts a novel halogen-free activity reinforcing agent produced by Shenzhen Jin Teng Longindustry Limited, has the function of an activator in the soldering flux, also has the function of a surfactant, and accords with RoHs indexes, wherein ST-200 and ST-400 are successful substitutes of active additives such as 2,3-dibromo 1,4-butylene glycol, 2,3-dibromosuccinic acid and the like, and the halogen-free activity reinforcing agent has the characteristics of no halogen, no benzene ring, good dissolving effect and the like; FR-500 is a good substitute of dibromobutenediol, has strong activity and high impedance, plays a certain role in bright and full soldering spots, and is a good surface active additive in all soldering fluxes. According to the invention, by using the novel halogen-free activity reinforcing agent, firstly, a bromine-containing covalent compound can be successfully replaced, the welding activity of the soldering flux is effectively improved, the interfacial tension when tin liquid is spread is reduced, and the tin liquid is favorably infiltrated, secondly, no strong corrosive functional groups such as halogen elements and carboxylic acid exist in the molecular structure of the activating agent, and no corrosion is caused to a welding base material, thirdly, the melting point is between 110 ℃ and 140 ℃, the activating agent is easy to decompose and vaporize at the conventional welding temperature of 380 +/-20 ℃, a lot of foams can be generated, the buffering and inhibiting effects are realized on splashing, the generated foams gradually disappear due to large interfacial tension, so that the residues are less, and fourthly, the activating agent does not contain any halogen element, and is an environment-friendly cleaning-free halogen-free reagent.
(5) The surfactant adopted by the invention is a non-ionic halogen-free surfactant, can replace a fluorine-containing high-efficiency surfactant, avoids the harm of fluorine to the environment, is beneficial to improving the insulation resistance in a non-ionic state, further improves the reliability of welding spots, effectively promotes the wetting and spreading of solder, has remarkable effects on the elimination, inhibition and defect-free control of bubbles or foam, and can effectively inhibit the splashing caused by the instantaneous explosion of high-pressure bubbles of soldering flux during the welding of the soldering tin wire. And a proper amount of antioxidant agent is added in the formula, so that the soldering flux is favorably over-oxidized under the high-temperature welding operation. The compound modified rosin resin is used as a carrier film forming agent, so that the advantages of various performances of the film forming agent are complementary, and the defect of the comprehensive performance of the soldering flux caused by the insufficient performance of a single rosin resin is avoided. According to the invention, the high-boiling-point solvent and the low-boiling-point solvent are adopted for compounding, the low-boiling-point solvent is beneficial to dissolving the high-activity covalent iodine activator, the surfactant, the antioxidant and the corrosion inhibitor, the damage and the loss of active ingredients caused by the fact that a solid auxiliary agent is directly added into high-temperature liquid rosin for melting are avoided, the low-boiling-point solvent is volatilized or vaporized in the high-temperature molten rosin due to a low boiling point, but the high-boiling-point solvent is not easy to volatilize, the other auxiliary agents dissolved in the solvent are more fully and uniformly mixed in the rosin, and the condition that the other auxiliary agents are locally and unevenly distributed in the rosin after the low-boiling-point solvent is volatilized is avoided, so that the uniformity and the stability of the quality and the performance of the soldering flux are improved. All reagents adopted by the invention are covalent compounds without any ionic substances, so that the splashing is small.
(6) The lead-free soldering tin wire soldering flux disclosed by the invention meets the halogen-free environment-friendly requirements related to European Union RoHS instruction and REACH instruction and the halogen-free requirements related to application of joint enterprise standard IPC J-STD-004B, is the soldering flux for the halogen-free cleaning-free soldering tin wire, is suitable for Sn-Cu and Sn-Ag-Cu lead-free solders, and has the advantages of high activity, high tin feeding speed, easiness in wetting, low corrosion, low residue, excellent splashing performance and insulation resistance of more than or equal to 1.0 and 10 10 Omega, the spreading rate is more than or equal to 80 percent, and the post-welding reliability of electronic and electric products and components thereof is ensured.
Detailed Description
The present invention will be described in further detail with reference to the following examples, but the scope of the present invention is not limited to the examples.
Example 1
The halogen-free no-clean lead-free soldering tin wire soldering flux comprises the following raw materials in percentage by weight:
taiwan does not contain 685 lead rosin 57.47%
Refined hydrogenated acrylic acid modified rosin 24.63%
Methylsuccinic acid 1.00%
Suberic acid 1.00%
High activity covalent iodine activator A1.50%
ST-200 1.50%
ST-400 2.00%
FR-500 1.50%
Surfynol 104E 0.10%
Antioxidant BHT 0.50%
Gasoline antioxidant 1010.50%
0.30 percent of benzotriazole
3.00 percent of propylene glycol ethyl ether
Ethylene glycol monomethyl ether 1.00%
Tetrahydrofurfuryl alcohol 2.00%
1.00 percent of propylene glycol propyl ether
Diethylene glycol hexyl ether 1.00%
The preparation method of the halogen-free no-clean lead-free soldering tin wire soldering flux comprises the following steps: adding the Taiwan lead-free 685 rosin and the refined hydrogenated acrylic acid modified rosin into a reactor at the same time, heating to 160 ℃, stirring and melting completely, keeping the temperature at about 155 ℃, adding a mixture of methylsuccinic acid, suberic acid, ST-200, ST-400 and FR-500, and stirring for 10-15 minutes to melt completely to obtain a molten compound material; and then completely dissolving the high-activity covalent iodine activator, surfynol 104E, antioxidant BHT, ciba antioxidant 1010 and benzotriazole in a compound solvent of propylene glycol ethyl ether/ethylene glycol monomethyl ether/tetrahydrofurfuryl alcohol/propylene glycol propyl ether/diethylene glycol hexyl ether to obtain a compound solution, finally adding the compound solution into a molten compound material, and continuously stirring for 20 minutes to fully dissolve and uniformly mix the components to prepare the halogen-free and cleaning-free lead-free soldering tin wire soldering flux.
The flux of this example was filled in a hollow rod of snag3.0cu0.5 having a core wire of 1.2% to prepare a solder wire having a wire diameter of 0.8mm, and performance tests such as spattering, weldability, spreading ratio, copper plate corrosivity, post-soldering surface insulation resistance were performed, and the test results are shown in table 1.
Example 2
The halogen-free no-clean lead-free soldering tin wire soldering flux comprises the following raw materials in percentage by weight:
70.56 percent of refined hydrogenated rosin
Istman perhydrogenated rosin AXE 17.64%
2,2-dimethylolpropionic acid 1.00%
Adipic acid 1.30%
Sebacic acid 1.70%
High activity covalent iodine activator A1.00%
ST-200 1.00%
FR-500 2.00%
Oleyl alcohol polyoxyethylene ether 0.30%
Dynol 604 0.10%
Antioxidant BHT 0.30%
0.10 percent of benzotriazole
Ethylene glycol monomethyl ether 2.00%
Propylene glycol butyl ether 1.00%
The preparation method of the halogen-free no-clean lead-free soldering tin wire soldering flux comprises the following steps: adding refined hydrogenated rosin and Istman perhydrogenated rosin AXE into a reactor at the same time, heating to 140 ℃, stirring and melting completely, keeping the temperature at 140 ℃, adding a mixture of 2,2-dimethylolpropionic acid, adipic acid, sebacic acid, ST-200 and FR-500, and stirring for 10-15 minutes to completely melt the mixture to obtain a molten compound material; and then completely dissolving the high-activity covalent iodine activator, oleyl alcohol polyoxyethylene ether, dynol 604, antioxidant BHT and benzotriazole in the compound solvent of ethylene glycol monomethyl ether/propylene glycol butyl ether to obtain a compound solution, finally adding the compound solution into the molten compound material, and continuously stirring for 15-20 minutes to fully dissolve and uniformly mix the components to prepare the halogen-free and cleaning-free lead-free soldering tin wire soldering flux.
The flux of this example was filled in a hollow rod of snag3.0cu0.5 having a core wire of 2.2% to prepare a solder wire having a wire diameter of 0.15mm, and performance tests such as spattering, weldability, spreading ratio, copper plate corrosivity, post-soldering surface insulation resistance were performed, and the test results are shown in table 1.
Example 3
The halogen-free no-clean lead-free soldering tin wire soldering flux comprises the following raw materials in percentage by weight:
refined hydrogenated rosin 28.23%
Istman perhydrogenated rosin AXE 28.23%
Taiwan 685 No-lead rosin 28.24%
Myristic acid 2.00%
2-Pyridinecarboxylic acid 1.50%
1.00 percent of dimethylolbutyric acid
Glutaric acid 1.50%
High activity covalent iodine activator A1.60%
ST-400 2.00%
Surfynol AD01 0.50%
Surfynol DF110D 0.50%
Antioxidant BHT 0.60%
0.60 percent of benzotriazole
Propylene glycol monomethyl ether 1.50%
Ethanolamine 0.60%
Diethylene glycol methyl ether 1.40%
Tripropylene glycol butyl ether 1.00%
The preparation method of the halogen-free no-clean lead-free soldering tin wire soldering flux comprises the following steps: adding refined hydrogenated rosin, eastman perhydro pine hydrogenated rosin AXE and Taiwan 685 lead-free rosin into a reactor at the same time, heating to 155 ℃, stirring and melting completely, keeping the temperature at about 150 ℃, adding a mixture of myristic acid, 2-picolinic acid, dimethylol butyric acid, glutaric acid and ST-400, and stirring for 10-15 minutes to melt completely to obtain a molten compound material; and then completely dissolving the high-activity covalent iodine activator, surfynol AD01, surfynol DF110D, antioxidant BHT and benzotriazole in a compound solvent of propylene glycol monomethyl ether/ethanolamine/diethylene glycol methyl ether/tripropylene glycol butyl ether to obtain a compound solution, finally adding the compound solution into the molten compound material, and continuously stirring for 15-20 minutes to fully dissolve and uniformly mix the components to prepare the halogen-free cleaning-free lead-free soldering tin wire soldering flux.
The flux of this example was filled in a hollow rod of sncu0.7 with a core wire of 3.0% to prepare a wire solder of 2.0mm diameter, and the test results were shown in table 1, where the wire solder was subjected to performance tests such as spattering, weldability, spreading ratio, copper plate corrosivity, post-soldering surface insulation resistance, and the like.
Example 4
The halogen-free no-clean lead-free soldering tin wire soldering flux comprises the following raw materials in percentage by weight:
istman perhydrogenated rosin AXE 24.30%
Fully hydrogenated rosin RHR-3130HS 24.10%
16.20 percent of refined hydrogenated acrylic acid modified rosin
16.20 percent of water white rosin
Hexadecanoic acid 4.00%
2.50 percent of p-hydroxyphenylacetic acid
1.50 percent of mixed dibasic acid
Glutaric anhydride 2.00%
High activity covalent iodine activator A1.10%
FR-500 0.50%
Surfynol DM20 0.60%
Gasoline antioxidant 1010.0%
1.00 percent of benzotriazole
2.00 percent of propylene glycol ethyl ether
Tripropylene glycol methyl ether 1.50%
Dipropylene glycol butyl ether 2.50%
The preparation method of the halogen-free no-clean lead-free soldering tin wire soldering flux comprises the following steps: simultaneously adding Istman perhydrogenated rosin AXE, perhydrogenated rosin RHR-3130HS, refined hydrogenated acrylic acid modified rosin and water white rosin into a reactor, heating to 155 ℃, stirring and melting completely, keeping the temperature at about 155 ℃, adding a mixture of hexadecanoic acid, p-hydroxyphenylacetic acid, mixed dibasic acid, glutaric anhydride and FR-500, stirring for 10-15 minutes, and melting completely to obtain a molten compound material; and then completely dissolving the high-activity covalent iodine activator, surfynol DM20, ciba antioxidant 1010 and benzotriazole in a compound solvent of propylene glycol ethyl ether/tripropylene glycol methyl ether/dipropylene glycol butyl ether to obtain a compound solution, finally adding the compound solution into the molten compound material, and continuously stirring for 15-20 minutes to fully dissolve and uniformly mix the components to prepare the halogen-free and cleaning-free lead-free soldering tin wire soldering flux.
The flux of this example was filled into a hollow rod of snag0.3cu0.7 having a core wire of 4.5% to prepare a solder wire having a wire diameter of 1.0mm, and performance tests such as spattering, weldability, spreading ratio, copper plate corrosivity, and post-soldering surface insulation resistance were performed, and the test results are shown in table 1.
The above examples 1 to 4 were subjected to the respective performance tests of spattering ratio, weldability, expansion ratio, copper plate corrosion, post-weld surface insulation resistance and the like in accordance with the relevant test methods specified in International Standard IPC-TM-650 and the like, and the test results are shown in Table 1.
Table 1 soldering flux performance testing list table for soldering tin wire
As can be seen from Table 1, the halogen-free composition of the present invention is free of halogenCleaning soldering tin wire flux without F, cl, br and F - +Cl - +Br - +I - Less than 500ppm, meets RoHS instruction and REACH instruction, meets the halogen-free requirement of IPC J-STD-004B, is suitable for Sn-Cu series and Sn-Ag-Cu series lead-free solder wires with different welding cores and different wire diameters, has good spot welding and drag welding performances, small splashing, low corrosion, spreading rate of more than 80 percent and surface insulation resistance of more than 10 percent 10 Omega, satisfies the international standard IPC-TM-650 surface insulation resistance of more than 10 8 Omega requirements.
Claims (3)
1. The halogen-free cleaning-free lead-free soldering tin wire soldering flux is characterized in that: the raw materials comprise the following components in percentage by weight:
2.0 to 10.0 percent of compound organic carboxylic acid
High-activity covalent iodine activator 0.1-1.5%
0.5 to 5.0 percent of halogen-free activity reinforcing agent
0.1 to 1.0 percent of surfactant
0.1 to 1.0 percent of antioxidant
0.1 to 1.0 percent of corrosion inhibitor
3.0 to 8.0 percent of compound solvent
Compound modified rosin resin surplus
The compound organic carboxylic acid is a combination of more than two of 2-pyridine carboxylic acid, p-hydroxyphenylacetic acid, 2,2-dimethylolpropionic acid, dimethylolbutyric acid, tetradecanoic acid, hexadecanoic acid, methylsuccinic acid, glutaric anhydride, adipic acid, suberic acid, sebacic acid, mixed dibasic acid and malic acid;
the high-activity covalent iodine activator is a high-activity covalent iodine activator A1 sold by Shenzhen Hongshouye Limited;
the halogen-free activity reinforcing agent is one or more of ST-200, ST-400 and FR-500 sold by Shenzhen, jin Teng Longindustry Limited;
the surfactant is one or more of oleyl alcohol polyoxyethylene ether, surfynol 104E, dynol 604, surfynol AD01, surfynol DM20 and Surfynol DF 110D;
the antioxidant is one or two of a gasoline engine antioxidant 1010 and an antioxidant BHT;
the corrosion inhibitor is benzotriazole;
the compound solvent is a combination of a low-boiling point solvent and a high-boiling point solvent; the low-boiling point solvent is one or more of ethylene glycol monomethyl ether, propylene glycol monomethyl ether and propylene glycol ethyl ether, and the high-boiling point solvent is one or more of tetrahydrofurfuryl alcohol, ethanolamine, propylene glycol propyl ether, propylene glycol butyl ether, diethylene glycol methyl ether, tripropylene glycol butyl ether, diethylene glycol hexyl ether and dipropylene glycol butyl ether;
the compound modified rosin resin is a combination of more than two of refined hydrogenated rosin, eastman perhydrogenated rosin AX-E, perhydrogenated rosin RHR-3130HS, refined hydrogenated acrylic acid modified rosin, taiwan 685 leadless rosin and water white rosin.
2. The preparation method of the halogen-free and cleaning-free lead-free solder wire soldering flux as recited in claim 1, characterized by comprising the following steps:
(1) Adding the compound modified rosin resin into a reactor, heating, stirring and melting completely;
(2) Adding compound organic carboxylic acid and halogen-free activity reinforcing agent into the compound modified rosin resin melted in the step (1), heating, stirring at constant temperature and melting completely to obtain compound material;
(3) Dissolving a high-activity covalent iodine activator, a surfactant, an antioxidant and a corrosion inhibitor in a compound solvent to obtain a compound solution;
(4) And (3) adding the compound solution prepared in the step (3) into the compound material prepared in the step (2), heating and continuously stirring at constant temperature until the compound material and the compound solution are uniformly mixed to obtain the halogen-free and cleaning-free lead-free soldering tin wire soldering flux.
3. The preparation method of the halogen-free and cleaning-free lead-free solder wire flux according to claim 2, wherein the heating temperature of the compound modified rosin resin in the step (1) is 150 ± 10 ℃; the heating constant temperature of the compound material prepared in the step (2) is 150 +/-10 ℃; and (4) the heating constant temperature of the halogen-free no-clean lead-free solder wire soldering flux prepared in the step (4) is 150 +/-10 ℃.
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| CN107442970A (en) * | 2017-08-10 | 2017-12-08 | 东北大学 | Low temperature No-clean Flux Used for Making Solder Paste and preparation method thereof |
| CN108465984A (en) * | 2018-06-28 | 2018-08-31 | 广东剑鑫科技股份有限公司 | A kind of Halogen water-soluble flux and preparation method thereof |
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| EP0324194A1 (en) * | 1988-01-12 | 1989-07-19 | KERNER, Rudolf A. | Process for manufacturing electronic components using a carboxylic acid based soldering flux |
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| CN107442970A (en) * | 2017-08-10 | 2017-12-08 | 东北大学 | Low temperature No-clean Flux Used for Making Solder Paste and preparation method thereof |
| CN108465984A (en) * | 2018-06-28 | 2018-08-31 | 广东剑鑫科技股份有限公司 | A kind of Halogen water-soluble flux and preparation method thereof |
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