CN104858571B - A kind of stannum bismuth system lead-free tin cream halogen-free flux and preparation method thereof - Google Patents

A kind of stannum bismuth system lead-free tin cream halogen-free flux and preparation method thereof Download PDF

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CN104858571B
CN104858571B CN201510314559.6A CN201510314559A CN104858571B CN 104858571 B CN104858571 B CN 104858571B CN 201510314559 A CN201510314559 A CN 201510314559A CN 104858571 B CN104858571 B CN 104858571B
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free
acid
tin cream
system lead
bismuth system
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CN201510314559.6A
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CN104858571A (en
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刘家党
肖德成
肖德华
肖大为
肖涵飞
肖健
肖雪
邓忠庆
邱海波
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深圳市同方电子新材料有限公司
深圳市同方新源科技有限公司
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    • 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
    • B23K35/3612Selection 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 organic 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
    • B23K35/40Making wire or rods for soldering or welding

Abstract

The present invention provides a kind of stannum bismuth system lead-free tin cream halogen-free flux and preparation method thereof.Described scaling powder is made up of 20 ~ 47% Colophonium, 8 ~ 20% viscosifier, 0.5 ~ 12% antioxidant, 4 ~ 15% organic acid, 0.2 ~ 3% ethylhexyl isooctyl acid, 6 ~ 14% organic amines, 0.5 ~ 8% surfactant, 4 ~ 10% thixotropic agent and balance solvent.The scaling powder of the present invention passes through the reactive systems of optimized choice scaling powder, so that the tin cream of the scaling powder of invention and stannum bismuth system unleaded glass putty configuration does not only contain any fluorine, chlorine, bromine, iodine and astatine halogens, and show good solderability in soldering, the full light of solder joint after soldering, not produce black oxide, surface insulation resistance high, is particularly well-suited to the erection welding that brazing temperature requires relatively low electronic devices and components.

Description

A kind of stannum bismuth system lead-free tin cream halogen-free flux and preparation method thereof

Technical field

The present invention relates to technical field of soldering paste, especially relate to a kind of stannum bismuth system lead-free tin cream halogen-free flux And preparation method thereof.

Background technology

With the fast development of electronics industry, the lead-free tin cream as electronic devices and components and circuit board connecting material obtains extensively General application.At present, the main flow lead-free tin cream alloying component on market is mainly Sn-3.0Ag-0.5Cu (writing a Chinese character in simplified form SAC305), its Fusing point more than 217 DEG C, also up to more than 240 DEG C of corresponding reflow soldering temperature, however some more sensitive to temperature or The poor soldered field of person's thermal shock resistance (as LED adorns industry and radiator etc.), its welding temperature can not be too high, Therefore SAC305 lead-free tin cream cannot meet soldered and require.Therefore, the relatively low stannum bismuth system lead-free tin cream of fusing point becomes The preferred material in soldered field.However, the bismuth in stannum bismuth tin cream is easy to occur oxidation formation black in brazing process Color oxide, this black oxide had both affected the outward appearance of solder joint, reduced the surface insulation resistance of solder joint simultaneously, or even deteriorated solder joint Mechanical property.At present industry is mainly using having highly active organohalogen compounds (as dimethylamine hydrochloride, cyclohexylamine hydrochloric acid Salt, dibromo butene glycol) reduce, to remove, the black oxide being formed in brazing process, such as Chinese patent CN102069323B is public A kind of middle temperature tin alloy soldering paste of the through hole coating operations opened, employs dibromo butene glycol;Chinese patent A kind of halogen-free and lead-free low temperature tin cream scaling powder disclosed in CN104416298A, employs the superpower ammonium acid fluoride of activity as activity Agent.But although such highly active organohalogen compounds can effectively remove black oxide, auxiliary solder climbs stannum rapidly, but Be a large amount of organohalogen compounds using in brazing process if having little time to decompose and volatilizing and remain in solder joint, this is by butt welding The mechanical property of point and electric property bring potential harmful effect, such as butt welding point and substrate generation burn into reduction surface exhausted Edge resistance and cause short circuit etc..Therefore, it is highly desirable to carry out formula to the current stannum bismuth system lead-free tin cream scaling powder using Improve.

Content of the invention

For deficiency of the prior art, the purpose of the present invention is to overcome the deficiencies in the prior art, provide a kind of low cost, Low melting point, halogen-free, the bright full stannum bismuth system lead-free tin cream of solder joint.This stannum bismuth system lead-free tin cream and main flow SAC305 phase Not only low cost, fusing point are low, little to the electronic devices and components hot injury of heat sensitive electronic and thermal shock resistance difference, and do not contain for ratio There are any fluorine, chlorine, bromine, iodine and astatine halogens, butt welding point corrosivity are little, no black oxidation in what is more important brazing process Thing generates, and solder joint light is full.

Present invention also offers a kind of preparation method of stannum bismuth system lead-free tin cream halogen-free flux.

The purpose of the present invention is realized by following technical proposal:

A kind of stannum bismuth system lead-free tin cream halogen-free flux, it is grouped into by the one-tenth of following weight percentage ratio:

Remaining is solvent.

Further optimally, described Colophonium is perhydrogenated rosin, water-white Colophonium, colourless Colophonium, 685 Colophonium, 610 Colophonium Compositionss with one or more of 604 Colophonium.

Further optimally, described viscosifier are P-105 resin, polybutene, polyisobutylene one or more combination.

Further optimally, described antioxidant is imidazoles, 2- ethyl imidazol(e) and 2,6- di-tert-butyl-4-methy phenol In the compositionss of one or more.

Further optimally, described organic acid be malonic acid, succinic acid, 1,3-propanedicarboxylic acid, adipic acid, decanedioic acid, benzoic acid, The compositionss of one or more of phthalic acid, terephthalic acids and NA anhydride.

Further optimally, described organic amine is ethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylene The compositionss of one or more of tetramine and hydroxyethylethylene diamine.

Further optimally, described surfactant is mono phosphoric acid ester isooctyl, phenyl glycidyl ether and polyoxyethylene The compositionss of one or more of glycerin ether.

Further optimally, described thixotropic agent is modified hydrogenated Oleum Ricini and the compositionss of ethylidene stearic amide;

Further optimally, described solvent is ethyl ethohexadiol, ethohexadiol, methyl pentanediol, TEG two The compositionss of one or more of methyl ether, diethylene glycol monohexyl ether and triethyl group carbitol ether.

A kind of preparation method of described stannum bismuth system lead-free tin cream halogen-free flux, comprises the steps:

(1) weigh above-mentioned each component by described percentage by weight standby;

(2) organic acid, ethylhexyl isooctyl acid and organic amine are put in reaction vessel, be heated to 100~120 DEG C, stir Mix 20~30 minutes, so that raw material is fully reacted, be prepared into the acid ammonium salt A of PH=6-7;

(3) add Colophonium, viscosifier, antioxidant and solvent in another reaction vessel, be heated to 140~180 DEG C, stir Mix 15~20 minutes so as to mix homogeneously;

(4) mixture obtaining above-mentioned steps (3) is cooled to 100~120 DEG C, is subsequently added above-mentioned steps (2) preparation Acid ammonium salt A and surfactant, stirring 15~20 minutes is so as to mix homogeneously;

(5) mixture obtaining above-mentioned steps (4) continues to be cooled to 50~80 DEG C, adds thixotropic agent, followed by height Fast mulser high speed emulsifying 10~20 minutes simultaneously stirs;

(6) mixture prepared by above-mentioned steps (5) is cooled to room temperature, and it is unleaded that standing obtained a kind of stannum bismuth system after 24 hours Tin cream halogen-free flux.

Present invention is generally directed to existing stannum bismuth system lead-free tin cream is using containing generation black oxygen after a large amount of halogen raw material and soldering Change and surface insulation resistance is relatively low and research and develop, the present invention adopts organic acid, ethylhexyl isooctyl acid (liquid acid) and organic amine elder generation It is neutralized reaction and prepares the neutral products acid ammonium salt that PH is 6~7, this acid ammonium salt does not corrode glass putty, no in storing process Cause viscosity over time, production organic acid, ethylhexyl isooctyl acid will be decomposed simultaneously in brazing process again and have Machine amine, greatly strengthen the activity of scaling powder, effectively removes the black oxide of bismuth;The Colophonium using can be in whole soldering Cover in journey in pad surface, stop reoxidizing of bismuth, prevent solder joint from blacking;The P-105 resin using and polybutene can drop The color of low Colophonium residue, makes the residue at solder joint edge as clear as crystal;The imidazoles using and 2- ethyl imidazol(e) can be in prickers Weldering process is reacted with the oxygen in air with being preferable over bismuth, stops the reaction of bismuth element.

The technology of the present invention has the advantage that and technique effect compared with having technology with oneself:

A) formulations of solder flux system does not contain any fluorine, chlorine, bromine, iodine and astatine halogens, and butt welding point corrosivity are little, surface Insulation resistance is high;

B) after soldering, solder joint does not generate black oxide, the full light of solder joint;

C) just 138 DEG C of the fusing point of stannum bismuth tin cream, therefore its brazing temperature is only at 180 DEG C about, to electronic devices and components hot injury Little, compared with main flow SAC305, do not contain noble silver, low cost, postwelding mechanical strength is high.

Specific embodiment

With reference to specific embodiment, the enforcement of the present invention is described in further detail, but the enforcement of the present invention and Protection not limited to this.

Embodiment 1

Scaling powder raw material:Perhydrogenated rosin 20g, P-105 resin 20g, imidazoles 0.5g, malonic acid 4g, ethylhexyl are different pungent Sour 3g, ethanolamine 3g, diethanolamine 3g, mono phosphoric acid ester isooctyl 8g, modified hydrogenated Oleum Ricini 4g, ethyl ethohexadiol 34.5g;

Preparation method:Malonic acid 4g, ethylhexyl isooctyl acid 3g, ethanolamine 3g and diethanolamine 3g are put into reaction hold In device, it is heated to 100 DEG C, stirring 20 minutes, so as to abundant react, is prepared into acid ammonium salt;Another reaction vessel add complete Hydrogenated rosin 20g, P-105 resin 20g, imidazoles 0.5g and ethyl ethohexadiol 34.5g, are heated to 140 DEG C, stir 15 minutes, make Its mix homogeneously;Then mixed liquor is cooled to 100 DEG C, adds above-mentioned acid ammonium salt and mono phosphoric acid ester isooctyl 8g, stir 15 minutes, Mix homogeneously;Continue to be cooled to 50 DEG C, add modified hydrogenated Oleum Ricini 4g, using high-speed emulsifying machine high speed emulsifying 10 minutes;? The mixture preparing afterwards is cooled to room temperature, and standing obtains a kind of stannum bismuth system lead-free tin cream after 24 hours and helps weldering with halogen-free Agent.

Embodiment 2

Scaling powder raw material:Water-white Colophonium 20g, colourless Colophonium 10g, P-105 resin 4g, polybutene 4g, 2- ethyl imidazol(e) 6g, 2,6 di tert butyl 4 methyl phenol 6g, succinic acid 5g, 1,3-propanedicarboxylic acid 5g, ethylhexyl isooctyl acid 0.2g, triethanolamine 8g, benzene Base glycidyl ether 0.2g, polyoxyethylene glycerol ether 0.3g, ethylidene stearic amide 10g, ethohexadiol 10g and methylpent Glycol 11.3g;

Preparation method:Succinic acid 5g, 1,3-propanedicarboxylic acid 5g, ethylhexyl isooctyl acid 0.2g, triethanolamine 8g are put into reaction In container, it is heated to 120 DEG C, stirring 30 minutes, so as to abundant react, is prepared into acid ammonium salt;Another reaction vessel adds Water-white Colophonium 20g, colourless Colophonium 10g, P-105 resin 4g, polybutene 4g, 2- ethyl imidazol(e) 6g and 2,6- di-t-butyl -4- first Base phenol 6g, ethohexadiol 10g and methyl pentanediol 11.3g, are heated to 180 DEG C, and stirring 20 minutes is so as to mix homogeneously; Then mixed liquor is cooled to 120 DEG C, adds above-mentioned acid ammonium salt, phenyl glycidyl ether 0.2g and polyoxyethylene glycerol ether 0.3g, stirs 20 minutes, mix homogeneously;Continue to be cooled to 80 DEG C, add ethylidene stearic amide 10g, using high speed emulsifying Machine high speed emulsifying 20 minutes;The mixture finally preparing is cooled to room temperature, and standing obtained a kind of stannum bismuth system after 24 hours Lead-free tin cream halogen-free flux.

Embodiment 3

Scaling powder raw material:685 Colophonium 10g, 610 Colophonium 20g, 604 Colophonium 17g, polyisobutylene 8g, imidazoles 0.5g, oneself two Sour 1g, decanedioic acid 2g, benzoic acid 2g, ethylhexyl isooctyl acid 3g, diethylenetriamine 14g, mono phosphoric acid ester isooctyl 2g, modified hydrogenated Oleum Ricini 2g, ethylidene stearic amide 3g, tetraethyleneglycol dimethyl ether 5g, diethylene glycol monohexyl ether 5g and triethyl group carbitol ether 5.5g;

Preparation method:By adipic acid 1g, decanedioic acid 2g, benzoic acid 2g, ethylhexyl isooctyl acid 3g and diethylenetriamine 14g Put in reaction vessel, be heated to 110 DEG C, stirring 25 minutes, so as to abundant react, is prepared into acid ammonium salt;In another reaction 685 Colophonium 10g, 610 Colophonium 20g, 604 Colophonium 17g, polyisobutylene 8g, imidazoles 0.5g, tetraethyleneglycol dimethyl ether is added in container 5g, diethylene glycol monohexyl ether 5g and triethyl group carbitol ether 5.5g, are heated to 160 DEG C, and stirring 18 minutes is so as to mix homogeneously; Then mixed liquor is cooled to 110 DEG C, adds above-mentioned acid ammonium salt and mono phosphoric acid ester isooctyl 2g, stir 18 minutes, mix homogeneously;Continue Continue and be cooled to 65 DEG C, add modified hydrogenated Oleum Ricini 2g and ethylidene stearic amide 3g, using high-speed emulsifying machine high speed emulsifying 15 minutes;The mixture finally preparing is cooled to room temperature, and standing obtains a kind of stannum bismuth system lead-free tin cream and uses after 24 hours Halogen-free flux.

Embodiment 4

Scaling powder raw material:Perhydrogenated rosin 30g, P-105 resin 5g, polybutene 2g, polyisobutylene 8g, imidazoles 1g, 2- second Base imidazoles 2g, 2,6 di tert butyl 4 methyl phenol 2g, phthalic acid 15g, ethylhexyl isooctyl acid 1g, triethanolamine 2g, Triethylene tetramine 1g, hydroxyethylethylene diamine 3g, mono phosphoric acid ester isooctyl 0.5g, modified hydrogenated Oleum Ricini 6g and ethyl ethohexadiol 21.5g;

Preparation method:By phthalic acid 15g, ethylhexyl isooctyl acid 1g, triethanolamine 2g, triethylene tetramine 1g and hydroxyl Ethylethylenediamine 3g puts in reaction vessel, is heated to 100 DEG C, and stirring 25 minutes, so as to abundant react, is prepared into sour ammonium Salt;In another reaction vessel add perhydrogenated rosin 30g, P-105 resin 5g, polybutene 2g, polyisobutylene 8g, imidazoles 1g, 2- ethyl imidazol(e) 2g, 2,6- di-tert-butyl-4-methy phenol 2g and ethyl ethohexadiol 21.5g, are heated to 160 DEG C, stir 20 points Clock is so as to mix homogeneously;Then mixed liquor is cooled to 110 DEG C, adds above-mentioned acid ammonium salt and mono phosphoric acid ester isooctyl 0.5g, stirring 18 minutes, mix homogeneously;Continue to be cooled to 70 DEG C, add modified hydrogenated Oleum Ricini 6g, using high-speed emulsifying machine high speed emulsifying 15 Minute;The mixture finally preparing is cooled to room temperature, and standing obtains a kind of stannum bismuth system lead-free tin cream no after 24 hours Halogen scaling powder.

Embodiment 5

Scaling powder raw material:Perhydrogenated rosin 10g, 604 Colophonium 15g, polybutene 10g, 2- ethyl imidazol(e) 8g, phthalic acid 2g, terephthalic acids 2g, NA anhydride 2g, ethylhexyl isooctyl acid 2g, diethanolamine 7g, mono phosphoric acid ester isooctyl 4g, modified hydrogenated castor Oleum Sesami 4g, tetraethyleneglycol dimethyl ether 10g and diethylene glycol monohexyl ether 24g;

Preparation method:By phthalic acid 2g, terephthalic acids 2g, NA anhydride 2g, ethylhexyl isooctyl acid 2g and diethanol Amine 7g puts in reaction vessel, is heated to 100 DEG C, and stirring 25 minutes, so as to abundant react, is prepared into acid ammonium salt;Another Perhydrogenated rosin 10g, 604 Colophonium 15g, polybutene 10g, 2- ethyl imidazol(e) 8g, tetraethyleneglycol dimethyl ether is added in reaction vessel 10g and diethylene glycol monohexyl ether 24g, is heated to 160 DEG C, and stirring 20 minutes is so as to mix homogeneously;Then mixed liquor is cooled to 110 DEG C, add above-mentioned acid ammonium salt and mono phosphoric acid ester isooctyl 4g, stir 20 minutes, mix homogeneously;Continue to be cooled to 70 DEG C, add Modified hydrogenated Oleum Ricini 4g, using high-speed emulsifying machine high speed emulsifying 10 minutes;The mixture finally preparing is cooled to room temperature, Standing obtained a kind of stannum bismuth system lead-free tin cream halogen-free flux after 24 hours.

According to electron trade standard SJ/T11273 2002 No clean liquid scaling powder, to foregoing invention embodiment 1 to reality The performance applying example 5 is estimated, and the results are shown in Table 1.

Table 1 embodiment 1 is to embodiment 5 assessment result

By table 1 assessment result it may be concluded that the stannum bismuth system lead-free tin cream halogen-free flux of the present invention has not Containing any fluorine, chlorine, bromine, iodine and astatine halogens, the rate of spread is high, and surface insulation resistance is high, and after soldering, solder joint is not simultaneously The advantage of black oxide occurs it is adaptable to temperature sensitive, thermal shock resistance is poor or the electronics that requires soldered Erection welding between components and parts.

Claims (10)

1. a kind of stannum bismuth system lead-free tin cream halogen-free flux is it is characterised in that it is grouped by the one-tenth of following weight percentage ratio Become:
Colophonium 20 ~ 47%
Viscosifier 8 ~ 20%
Antioxidant 0.5 ~ 12%
Organic acid 4 ~ 15%
Ethylhexyl isooctyl acid 0.2 ~ 3%
Organic amine 6 ~ 14%
Surfactant 0.5 ~ 8%
Thixotropic agent 4 ~ 10%;
Remaining is solvent.
2. stannum bismuth system lead-free tin cream halogen-free flux according to claim 1 is it is characterised in that described Colophonium is The compositionss of one or more of perhydrogenated rosin, water-white Colophonium, colourless Colophonium, 685 Colophonium, 610 Colophonium and 604 Colophonium.
3. stannum bismuth system lead-free tin cream halogen-free flux according to claim 1 is it is characterised in that described viscosifier For P-105 resin, polybutene, polyisobutylene one or more combination.
4. stannum bismuth system lead-free tin cream halogen-free flux according to claim 1 is it is characterised in that described antioxidation Agent is the compositionss of one or more in imidazoles, 2- ethyl imidazol(e) and 2,6 di tert butyl 4 methyl phenol.
5. stannum bismuth system lead-free tin cream halogen-free flux according to claim 1 is it is characterised in that described organic acid For in malonic acid, succinic acid, 1,3-propanedicarboxylic acid, adipic acid, decanedioic acid, benzoic acid, phthalic acid, terephthalic acids and NA anhydride Plant or several compositionss.
6. stannum bismuth system lead-free tin cream halogen-free flux according to claim 1 is it is characterised in that described organic amine For ethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylene tetramine and hydroxyethylethylene diamine one or more Compositionss.
7. stannum bismuth system lead-free tin cream halogen-free flux according to claim 1 is it is characterised in that live in described surface Property agent be one or more of mono phosphoric acid ester isooctyl, phenyl glycidyl ether and polyoxyethylene glycerol ether compositionss.
8. stannum bismuth system lead-free tin cream halogen-free flux according to claim 1 is it is characterised in that described thixotropic agent Compositionss for modified hydrogenated Oleum Ricini and ethylidene stearic amide.
9. stannum bismuth system lead-free tin cream halogen-free flux according to claim 1 is it is characterised in that described solvent is Ethyl ethohexadiol, ethohexadiol, methyl pentanediol, tetraethyleneglycol dimethyl ether, diethylene glycol monohexyl ether and triethyl group carbitol The compositionss of one or more of ether.
10. preparation claim 1 described in a kind of stannum bismuth system lead-free tin cream halogen-free flux method it is characterised in that Preparation process is as follows:
(1)Weigh above-mentioned each component by described percentage by weight standby;
(2)Organic acid, ethylhexyl isooctyl acid and organic amine are put in reaction vessel, are heated to 100 ~ 120 DEG C, stirring 20 ~ 30 minutes, so that raw material is fully reacted, be prepared into the acid ammonium salt A of PH=6-7;
(3)Add Colophonium, viscosifier, antioxidant and solvent in another reaction vessel, be heated to 140 ~ 180 DEG C, stirring 15 ~ 20 minutes so as to mix homogeneously;
(4)By above-mentioned steps(3)The mixture obtaining is cooled to 100 ~ 120 DEG C, is subsequently added above-mentioned steps(2)The sour ammonium of preparation Salt A and surfactant, stirring 15 ~ 20 minutes is so as to mix homogeneously;
(5)By above-mentioned steps(4)The mixture obtaining continues to be cooled to 50 ~ 80 DEG C, adds thixotropic agent, followed by high speed emulsifying Machine high speed emulsifying 10 ~ 20 minutes simultaneously stirs;
(6)Above-mentioned steps(5)The mixture of preparation is cooled to room temperature, obtains a kind of stannum bismuth system lead-free tin cream Halogen after standing Plain scaling powder.
CN201510314559.6A 2015-06-10 2015-06-10 A kind of stannum bismuth system lead-free tin cream halogen-free flux and preparation method thereof CN104858571B (en)

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CN105397343B (en) * 2015-11-26 2018-02-27 芜湖雅葆轩电子科技股份有限公司 Signal processing substrate tin cream and preparation method thereof
CN105364341B (en) * 2015-11-26 2018-02-27 芜湖雅葆轩电子科技股份有限公司 signal processing substrate
CN105364340B (en) * 2015-11-26 2018-02-27 芜湖雅葆轩电子科技股份有限公司 Signal processing substrate tin cream and preparation method thereof
CN106001997A (en) * 2016-06-05 2016-10-12 丘以明 Lead-free soldering paste and preparation method thereof
CN106001998A (en) * 2016-06-11 2016-10-12 丘以明 Flux paste special for unleaded tin-bismuth solder and preparation method thereof
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CN107150187A (en) * 2017-07-15 2017-09-12 芜湖乾凯材料科技有限公司 Scaling powder and preparation method thereof, solder(ing) paste and preparation method thereof
CN107825003B (en) * 2017-12-12 2020-01-10 云南锡业锡材有限公司 Preparation method of soldering flux for soldering paste and ultrasonic rapid cooling system thereof
CN108747090A (en) * 2018-06-21 2018-11-06 上海华庆焊材技术有限公司 One kind helping weldering glue and preparation method thereof, application
CN108817731B (en) * 2018-07-04 2020-04-10 中原工学院 Low-temperature halogen-free low-solid-content modified rosin type soldering flux and preparation method thereof

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