WO2013047602A1 - Aqueous composition for aluminum brazing - Google Patents

Aqueous composition for aluminum brazing Download PDF

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Publication number
WO2013047602A1
WO2013047602A1 PCT/JP2012/074741 JP2012074741W WO2013047602A1 WO 2013047602 A1 WO2013047602 A1 WO 2013047602A1 JP 2012074741 W JP2012074741 W JP 2012074741W WO 2013047602 A1 WO2013047602 A1 WO 2013047602A1
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aluminum
brazing
water
flux
mass
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PCT/JP2012/074741
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French (fr)
Japanese (ja)
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威 呂
知明 赤澤
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ハリマ化成株式会社
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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
    • B23K35/3601Selection 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
    • B23K35/3603Halide salts
    • B23K35/3605Fluorides
    • 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
    • B23K35/362Selection of compositions of fluxes
    • 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
    • B23K2103/00Materials to be soldered, welded or cut
    • B23K2103/08Non-ferrous metals or alloys
    • B23K2103/10Aluminium or alloys thereof

Definitions

  • the present invention relates to a water-based aluminum brazing composition used for brazing of an aluminum material.
  • aluminum and aluminum alloys (hereinafter, sometimes collectively referred to as “aluminum” in some cases) are used as forming materials for automobile heat exchangers and the like.
  • a method is generally employed in which, after assembling the members to be joined, a flux is applied to the surface of the members, dried, and heated to a brazing temperature.
  • a method in which a brazing composition in which a flux is dispersed in a dispersion medium together with a binder is prepared, and the obtained composition is applied to a member surface by means such as spray coating.
  • Patent Documents 1 to 3 disclose methacrylic acid ester polymers.
  • an acrylic resin such as a methacrylic ester polymer as a binder, as a dispersion medium for stably dispersing them, an organic solvent or a mixed solvent of an organic solvent and water is disclosed. Yes.
  • volatile organic solvents VOC
  • the “volatile organic compound” means an organic chemical substance that easily volatilizes in the atmosphere at normal temperature and pressure.
  • a binder such as a (meth) acrylic acid ester-based polymer maintains solubility in an aqueous dispersion medium by modifying a carboxyl group in the molecule with amino alcohols.
  • pH becomes low the ionic bond of carboxylate and amino alcohol will be inhibited, and a meth) acrylic acid ester type polymer will become insoluble. Therefore, a precipitate is generated in the brazing composition, and this precipitate causes a problem such as clogging the spray.
  • the problem of the present invention is that the adhesiveness of the flux to the member made of aluminum or aluminum alloy is good, and even if the content of the volatile organic compound is suppressed and the proportion of water in the dispersion medium is increased, the flux can be reduced.
  • An object of the present invention is to provide an aqueous aluminum brazing composition that can be stably dispersed.
  • An aqueous aluminum brazing composition comprising a fluoride flux, a binder, and a dispersion medium, wherein the binder is a water-soluble polymer, and the dispersion medium is water or water and a volatile organic compound.
  • An aqueous aluminum brazing composition in which the content of a volatile organic compound in the mixture is 10% by mass or less based on the total amount of the aqueous aluminum brazing composition.
  • the content ratio of the binder is 0.1 to 10% by mass in terms of solid content with respect to the total amount of the aqueous aluminum brazing composition.
  • the present invention good characteristics can be obtained as the adhesiveness of the flux to the aluminum or aluminum alloy member. Furthermore, even if the proportion of water in the dispersion medium is increased, it is possible to stably disperse the flux, thereby providing an aqueous aluminum brazing composition in which the content of volatile organic compounds is suppressed. Can do.
  • the aqueous aluminum brazing composition of the present invention contains a fluoride flux, a binder, and a dispersion medium.
  • Fluoride flux used in the present invention removes the oxide film on the aluminum surface during brazing.
  • the fluoride-based flux include various types used for brazing aluminum. Specifically, for example, potassium fluoroaluminate, potassium fluoride, aluminum fluoride, lithium fluoride, sodium fluoride, potassium fluoroaluminate-cesium complex (non-reactive cesium-based flux), cesium fluoroaluminate (non-reactive) Reactive cesium flux), potassium fluorozellese (reactive zinc substitution flux), cesium fluorozyere (reactive zinc substitution flux), and the like.
  • the fluoride-based flux the exemplified compounds may be used alone or in combination of two or more.
  • fluoride fluxes include, for example, “Nocolok (registered trademark) flux (potassium fluoroaluminate)”, “Nocolok (registered trademark) Sil flux” (fluoroaluminate) manufactured by Solvay. A mixture of potassium and metal silicon powder), “Nocolok (registered trademark) Cs flux (cesium-based flux)” and the like.
  • the binder used in the present invention is a water-soluble polymer.
  • the molecular weight of the water-soluble polymer is not particularly limited. However, a low molecular weight is required rather than a low molecular weight used as an anti-settling agent in conventional brazing compositions.
  • the adhesion of the flux to the aluminum member can be improved.
  • the molecular weight of the water-soluble polymer is preferably 50,000 to 300,000, more preferably 80000 to 200,000, as a weight average molecular weight according to the GPC method.
  • water-soluble polymer examples include polyvinyl alcohol, polyethylene oxide, water-based polyester resin, methyl cellulose, water-based epoxy resin, and the like. Since these water-soluble polymers are excellent in thermal decomposability, they tend to volatilize during brazing, and carbide residues are unlikely to remain.
  • polyvinyl alcohol is preferable as the binder used in the present invention.
  • a binder may be used independently and may use 2 or more types together.
  • the dispersion medium used in the present invention includes water alone or a mixture of water and VOC. In particular, it is preferable to use water alone as a dispersion medium.
  • the amount of VOC contained in the dispersion medium is set to be 10% by mass or less based on the total amount of the aqueous aluminum brazing composition. If the content of VOC is 10% by mass or less with respect to the total amount of the aqueous aluminum brazing composition, the composition is sufficiently “low VOC” compared to the conventional aluminum brazing composition. be able to.
  • the content ratio of VOC with respect to the total amount of the aqueous aluminum brazing composition is more preferably 5% by mass or less.
  • VOC Although it does not specifically limit as VOC, A thing with high compatibility with water is preferable. Specifically, methanol, ethanol, n-propyl alcohol, isopropyl alcohol, 1,3-butanediol, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol (MMB), etc.
  • Alcohols such as acetone, methyl ethyl ketone, isobutyl ketone, etc .; ethers such as diethyl ether; naphthenic alicyclic hydrocarbons; ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol butyl ether, diethylene glycol methyl ether, diethylene glycol Ethyl ether, diethylene glycol butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether Dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, glycol ethers such as dipropylene glycol monobutyl ether, and the like.
  • the blending amount of the fluoride flux, binder, and dispersion medium is not particularly limited as long as it can function as a water-based aluminum brazing composition.
  • the blending amount of the fluoride-based flux is preferably 5 to 50% by weight, more preferably 10 to 40% by weight, based on the total amount of the aqueous aluminum brazing composition, although it depends on the blending amount of the binder.
  • the blending amount of the fluoride-based flux is small, the amount of the aqueous aluminum brazing composition applied during brazing tends to be excessive.
  • the amount of the binder is preferably 0.1 to 10% by mass, more preferably 0.3 to 4% by mass, based on the total amount of the aqueous aluminum brazing composition, although it depends on the amount of fluoride flux. .
  • the blending amount of the binder is small, the effect of attaching the fluoride flux to the surface of the aluminum member may be reduced depending on the blending amount of the fluoride flux.
  • the amount of the binder is large, the viscosity of the aqueous aluminum brazing composition tends to increase.
  • the mass ratio between the fluoride-based flux and the binder is not particularly limited, but is preferably 99.5: 0.5 to 75:25, more preferably 99: 1 to 80:20, and 99: 1 to 90:10. Particularly preferred.
  • the mass ratio between the fluoride-based flux and the binder is not particularly limited, but is preferably 99.5: 0.5 to 75:25, more preferably 99: 1 to 80:20, and 99: 1 to 90:10. Particularly preferred.
  • the water-based aluminum brazing composition of the present invention can be blended with other additives as necessary within a range that does not impair the effects of the present invention.
  • additives include, for example, antioxidants such as dibutylhydroxytoluene (BHT); corrosion inhibitors such as benzotriazole; antifoaming agents such as silicone oil and glycerin; waxes, hardened oils, fatty acid amides, polyamides and the like Thickeners; coloring agents and the like.
  • the aqueous aluminum brazing composition of the present invention is spray-applied to an adherend heated to a high temperature, for example.
  • a coating film of flux and binder is formed on the brazed portion.
  • the composition for water-system aluminum brazing of this invention is used also as a material of the member for brazing mentioned later.
  • the aqueous aluminum brazing composition of the present invention can be supplied, for example, as a brazing member in a state where it is applied to the surface of an aluminum substrate and dried.
  • the base material is made of aluminum or an aluminum alloy, and the thickness thereof is not particularly limited, and can be appropriately set according to a desired application (formed product).
  • a brazing material is applied to the surface of the substrate. Examples of the brazing material include metallic silicon, silicon-aluminum alloys, alloys containing a small amount of magnesium, copper, germanium, and the like.
  • the aqueous aluminum brazing composition is applied to the substrate.
  • the coating method can be appropriately selected from, for example, a spray method, a roll coating method, a dipping method, and the like, but the spray method is particularly preferable.
  • the coating amount of the aqueous aluminum brazing composition is preferably 5 to 60 g, more preferably 10 to 40 g as a dry mass per 1 m 2 of the coated surface from the viewpoints of brazing and coating stability.
  • the brazing material and the aqueous aluminum brazing composition may be applied to only one surface of the base material surface or may be applied to both surfaces depending on the application. Moreover, when a base material has a certain amount of thickness, you may apply
  • the water-based aluminum brazing composition or brazing member of the present invention is used as a material for an automotive heat exchanger such as an evaporator or a capacitor mounted on a vehicle, and a molded product obtained (such as an automotive heat exchanger).
  • an automotive heat exchanger such as an evaporator or a capacitor mounted on a vehicle
  • a molded product obtained such as an automotive heat exchanger
  • Example 1 Flux and PVA were added to water and stirred to obtain an aqueous aluminum brazing composition. As shown in Table 1, the content ratio of each component with respect to the total amount of the composition is such that the flux is 5% by mass, the PVA is 0.4% by mass, the remaining amount is water, and the mass ratio of the flux to the binder (PVA) was 92.6: 7.4.
  • Example 2 to 10 and 12 to 17 An aqueous aluminum brazing composition was obtained in the same manner as in Example 1 except that the content ratios of the flux and PVA were set as shown in Table 1.
  • Example 11 A flux and PVA were added to a mixed dispersion medium of water and MMB, and the mixture was stirred to obtain an aqueous aluminum brazing composition. As shown in Table 1, the content ratio of each component with respect to the total amount of the composition is 30% by mass of flux, 2.2% by mass of PVA, 10% by mass of MMB, and the remaining amount of water. The mass ratio was 93.2: 6.8.
  • Reference Example 2 An aluminum brazing composition was obtained in the same manner as in Reference Example 1, except that the contents of the acrylic resin, flux, water, and MMB were set as shown in Table 1.
  • FIG. 1 shows an external view of a brazeability evaluation sample
  • FIG. 2 shows a side view of the evaluation sample after heating to a brazing temperature.
  • the brazeability evaluation sample 10 has a width W 1 and W 2 of 25 mm, a length L 1 and L 2 of 70 mm, and a thickness of 2.0 mm (aluminum flat plate 11) and 0.8 mm (aluminum flat plate 12). Two aluminum flat plates 11 and 12 and a stainless steel wire 13 having a diameter of 1.6 mm are provided.
  • the first aluminum flat plate 11 is rolled with an aluminum-silicon alloy (JIS-A4047P, 0.2 mm) serving as a brazing material surface on the upper surface and pure aluminum (JIS-A1050P, 1.8 mm) serving as a core material on the lower surface.
  • a flat plate was used.
  • As the second aluminum flat plate 12 a flat plate made of pure aluminum (JIS-A1050P) was used.
  • the first aluminum flat plate 11 was heated to 200 ° C., and an aluminum brazing composition was applied to the surface of the brazing material to form a coating layer on the surface.
  • an aluminum brazing composition those prepared in the above-mentioned Examples, Comparative Examples and Reference Examples were used.
  • one end edge E 1 on the long side of the second aluminum flat plate 12 is abutted against the surface (brazing material surface) 14 of the first aluminum flat plate 11 so that the end edge E 1 is the first end. It was placed along the length L 1 of the aluminum flat plate 11. At this time, one corner C 1 of the edge E 1 of the second aluminum flat plate 12 was brought into contact with the surface 14 of the first aluminum flat plate 11. Further, the other corner C 2 side of the edge E 1 was brought into contact with the stainless steel wire 13 disposed on the surface 14 of the first aluminum flat plate 11.
  • the said evaluation sample 10 was heated to 600 degreeC which is brazing temperature, and the 1st aluminum flat plate 11 and the 2nd aluminum flat plate 12 were brazed.
  • the evaluation of the brazing property is better as the filling length L 3 (see FIG. 2) of the brazing material after brazing is larger.
  • the maximum value of the filling length L 3 is 45 mm corresponding to the distance D described above.
  • the evaluation criteria for brazeability are as follows. A: When the filling length L 3 is 40 mm or more and the brazing property is very good. B: When the filling length L 3 is 20 mm or more and less than 40 mm and brazing properties that are practically acceptable are obtained. C: When the filling length L 3 is less than 20 mm and the brazability is insufficient.
  • FIG. 3 is a schematic diagram showing an evaluation method for adhesiveness.
  • the sample 20 for spray adhesion evaluation includes an aluminum flat plate 21 and a coating layer 22 formed on one surface thereof.
  • a flat plate made of pure aluminum (JIS-A1050P) having a length of 150 mm and a width of 70 mm was used.
  • the coating layer 22 was formed by spray-coating the aluminum brazing composition on the surface of the aluminum flat plate 21 previously heated to 200 ° C. and removing the dispersion medium by heating.
  • the aluminum brazing composition those prepared in the above Examples, Comparative Examples and Reference Examples were used, and the coating amount was set to 15 g / m 2 .
  • the aluminum flat plate 21 on which the coating layer 22 was formed was placed on a flat table with the coating layer 22 facing upward.
  • the surface of the aluminum flat plate 21 is placed on the surface of the coating layer 22 while placing a plastic eraser 23 ("uni plastic eraser" manufactured by Mitsubishi Pencil Co., Ltd.) and applying a load of 1 kgf (9.8 N) in the vertical direction.
  • a plastic eraser 23 uni plastic eraser manufactured by Mitsubishi Pencil Co., Ltd.
  • a load of 1 kgf (9.8 N) in the vertical direction. was reciprocated in one direction.
  • the number of reciprocations when the coating layer 22 was completely scraped by the plastic eraser friction (hereinafter simply referred to as “the number of reciprocations”) was counted.
  • the adhesion is better as the number of reciprocations is larger.
  • the evaluation criteria for adhesion are as follows. A +: When the number of reciprocations is 10 times or more and the adhesion is very good. A: The number of reciprocations is 4 times or more and less than 10 times, and the adhesion is good. B: The number of reciprocations is 2 times or more and less than 4 times, and practically acceptable adhesion can be obtained. C: When the number of reciprocations is less than 2 and adhesion is insufficient.
  • Viscosity For each of the compositions for aluminum brazing in the above Examples, Comparative Examples, and Reference Examples, the viscosity is measured using an E-type viscometer (model number “TV-22” manufactured by Toki Sangyo Co., Ltd.). Thus, it was evaluated whether it was suitable for spray application.
  • the measurement conditions were a measurement temperature of 25 ° C. and a rotation speed of the measurement sample of 100 rotations / minute.
  • the measurement results of the viscosity and the criteria for determining whether or not to use for spray coating are as follows. A: When the viscosity is 200 mPa ⁇ s ⁇ 1 or less and is extremely suitable for spray coating. B: When the viscosity is more than 200 mPa ⁇ s ⁇ 1 and 500 mPa ⁇ s ⁇ 1 or less and is practically acceptable for application to spray coating. C: When the viscosity is not suitable for spray coating exceeding 500 mPa ⁇ s ⁇ 1 .
  • the degree of VOC content was ranked in the following stages. A: When the content ratio of VOC is 5% by mass or less and the low VOC property is very good. B: When the content ratio of VOC exceeds 5% by mass and is 10% by mass or less. C: The content ratio of VOC exceeds 10% by mass, and the amount of VOC is not sufficiently reduced.
  • Stability was evaluated according to the following criteria. A: When the ratio of the residue is 0.05% by mass or less and the stability is very good. B: The proportion of the residue is more than 0.05% by mass and 0.2% by mass or less, and practically acceptable stability is obtained. C: The ratio of the residue exceeds 0.2% by mass and the stability is insufficient.
  • compositions of the present invention are all good in brazeability, adhesion, viscosity, low VOC property and stability.
  • compositions of Comparative Examples 1 to 3 have a high VOC content and are inferior in any of brazing, adhesion, and viscosity.

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Abstract

An aqueous composition for aluminum brazing according to the present invention comprises a fluoride flux, a binder and a dispersion medium, wherein the binder is a water-soluble polymer, the dispersion medium is water or a mixture of water and a volatile organic compound, and the content of the volatile organic compound in the mixture is 10 mass% or less relative to the total amount of the aqueous composition for aluminum brazing.

Description

水系アルミニウムろう付用組成物Water-based aluminum brazing composition
 本発明は、アルミニウム材料のろう接に用いる水系アルミニウムろう付用組成物に関する。 The present invention relates to a water-based aluminum brazing composition used for brazing of an aluminum material.
 自動車用熱交換器などの形成材料には、軽量化の観点から、アルミニウムやアルミニウム合金(以下、これらをまとめて単に「アルミニウム」と記載する場合がある)が用いられている。従来、アルミニウム製の部材をろう付により接合する際には、接合する部材同士を組み立てた後に、部材表面にフラックスを塗布して乾燥させ、ろう付温度に加熱する方法が一般的である。 From the viewpoint of weight reduction, aluminum and aluminum alloys (hereinafter, sometimes collectively referred to as “aluminum” in some cases) are used as forming materials for automobile heat exchangers and the like. Conventionally, when joining aluminum members by brazing, a method is generally employed in which, after assembling the members to be joined, a flux is applied to the surface of the members, dried, and heated to a brazing temperature.
 しかし、自動車用熱交換器のように、構造が複雑なものをろう付する場合には、部材を組み立てた後で接合部位にフラックスを塗布することが困難である。そこで、近年、アルミニウム製の部材の表面に予めフラックスを塗布しておき、その後、接合する部材同士を組み立てて、炉内でろう付温度に加熱するろう付方法が採用されている。また、このような用途において、フラックスには、フッ化物系フラックスが広く用いられている。フッ化物系フラックスはアルミニウムに対する腐食性を示さないことから、ろう付後の洗浄除去操作が不要である。このため、自動車用熱交換器のような部材のろう付に適しており、ろう付設備の連続運転にも適している。 However, when brazing a complicated structure such as a heat exchanger for automobiles, it is difficult to apply a flux to the joint portion after assembling the members. Therefore, in recent years, a brazing method has been adopted in which a flux is previously applied to the surface of an aluminum member, and then the members to be joined are assembled and heated to a brazing temperature in a furnace. In such applications, fluoride fluxes are widely used as the flux. Since the fluoride-based flux does not exhibit corrosiveness to aluminum, no washing and removing operation after brazing is required. For this reason, it is suitable for brazing of members, such as a heat exchanger for vehicles, and is also suitable for continuous operation of brazing equipment.
 ろう付の精度を高めるには、アルミニウム製部材の表面においてフラックスが強固に付着し、摩擦や振動によって脱落することを抑制する必要がある。そこで、フラックスを、バインダとともに分散媒に分散させたろう付用組成物を調製し、得られた組成物をスプレー塗布などの手段によって部材表面に塗布する方法が用いられている。 In order to increase the accuracy of brazing, it is necessary to prevent the flux from firmly adhering to the surface of the aluminum member and falling off due to friction or vibration. Accordingly, a method is used in which a brazing composition in which a flux is dispersed in a dispersion medium together with a binder is prepared, and the obtained composition is applied to a member surface by means such as spray coating.
 このような塗布方法に用いるバインダとして、特許文献1~3は、メタクリル酸エステル系重合体を開示している。また、メタクリル酸エステル系重合体などのアクリル樹脂をバインダとして使用する場合において、これらを安定して分散させるための分散媒としては、有機溶媒や、有機溶媒と水との混合溶媒を開示している。 As the binder used in such a coating method, Patent Documents 1 to 3 disclose methacrylic acid ester polymers. In addition, in the case of using an acrylic resin such as a methacrylic ester polymer as a binder, as a dispersion medium for stably dispersing them, an organic solvent or a mixed solvent of an organic solvent and water is disclosed. Yes.
特開2009-208129号公報JP 2009-208129 A 特開2009-166122号公報JP 2009-166122 A 特開2009-142870号公報JP 2009-142870 A
 近年、環境問題に対する関心の高まりから、ろう付用組成物に用いられる分散媒についても、揮発性有機溶剤(Volatile Organic Compounds:VOC)の含有量をできる限り低減させること、あるいは有機溶媒から水に切り替えることが求められている。なお、「揮発性有機化合物」とは、常温常圧で大気中に容易に揮発する有機化学物質のことをいう。 In recent years, due to increasing interest in environmental issues, the content of volatile organic solvents (VOC) has been reduced as much as possible for dispersion media used in brazing compositions, or from organic solvents to water. There is a need to switch. The “volatile organic compound” means an organic chemical substance that easily volatilizes in the atmosphere at normal temperature and pressure.
 しかし、分散媒中の水の割合が高くなると、フッ化物系フラックスから水素イオン(H+)が溶出しやすくなり、ろう付用組成物のpHが経時的に低くなる。pHが低くなると、バインダの溶解性や分散性が顕著に低下し、ろう付用組成物に沈殿物が生じるおそれがある。例えば、(メタ)アクリル酸エステル系重合体のようなバインダは、分子中のカルボキシル基をアミノアルコール類などで修飾することにより、水系分散媒中での溶解性を維持している。pHが低くなると、カルボキシラートとアミノアルコール類とのイオン結合が阻害され、メタ)アクリル酸エステル系重合体が不溶化する。そのため、ろう付用組成物中に沈殿物が生じ、この沈殿物は、スプレーを目詰まりさせるといった不具合の要因となる。 However, as the proportion of water in the dispersion medium increases, hydrogen ions (H + ) are likely to elute from the fluoride flux, and the pH of the brazing composition decreases with time. When pH becomes low, the solubility and dispersibility of a binder will fall remarkably, and there exists a possibility that a deposit may arise in the brazing composition. For example, a binder such as a (meth) acrylic acid ester-based polymer maintains solubility in an aqueous dispersion medium by modifying a carboxyl group in the molecule with amino alcohols. When pH becomes low, the ionic bond of carboxylate and amino alcohol will be inhibited, and a meth) acrylic acid ester type polymer will become insoluble. Therefore, a precipitate is generated in the brazing composition, and this precipitate causes a problem such as clogging the spray.
 本発明の課題は、アルミニウムまたはアルミニウム合金製の部材に対するフラックスの密着性が良好であり、かつ揮発性有機化合物の含有量を抑制して分散媒中の水の割合を多くしても、フラックスを安定して分散させることができる水系アルミニウムろう付用組成物を提供することである。 The problem of the present invention is that the adhesiveness of the flux to the member made of aluminum or aluminum alloy is good, and even if the content of the volatile organic compound is suppressed and the proportion of water in the dispersion medium is increased, the flux can be reduced. An object of the present invention is to provide an aqueous aluminum brazing composition that can be stably dispersed.
 本発明者らは、上記課題を解決するべく鋭意検討を行った結果、以下の構成からなる解決手段を見出し、本発明を完成するに至った。
 (1)フッ化物系フラックスと、バインダと、分散媒とを含む水系アルミニウムろう付用組成物であって、前記バインダが水溶性ポリマーであり、前記分散媒が水または水と揮発性有機化合物との混合物であり、前記混合物中の揮発性有機化合物の含有量が、水系アルミニウムろう付用組成物総量に対して10質量%以下である水系アルミニウムろう付用組成物。
 (2)前記水溶性ポリマーが、ポリビニルアルコールである、(1)に記載の水系アルミニウムろう付用組成物。
 (3)前記フッ化物系フラックスと前記バインダとの含有量の比が、質量比で99.5:0.5~75:25である、(1)または(2)に記載の水系アルミニウムろう付用組成物。
 (4)前記バインダの含有割合が、固形分換算で、水系アルミニウムろう付用組成物の総量に対して0.1~10質量%である、(1)~(3)のいずれかの項に記載の水系アルミニウムろう付用組成物。
 (5)上記(1)~(4)のいずれかの項に記載の水系アルミニウムろう付用組成物を、アルミニウムの基材表面の片面または両面に塗布して得られる、ろう付用部材。
 (6)前記水系アルミニウムろう付用組成物の塗布量が、前記アルミニウムの基材表面1m2あたり、乾燥質量として5~60gである、(5)に記載のろう付用部材。
As a result of intensive studies to solve the above problems, the present inventors have found a solution means having the following configuration, and have completed the present invention.
(1) An aqueous aluminum brazing composition comprising a fluoride flux, a binder, and a dispersion medium, wherein the binder is a water-soluble polymer, and the dispersion medium is water or water and a volatile organic compound. An aqueous aluminum brazing composition in which the content of a volatile organic compound in the mixture is 10% by mass or less based on the total amount of the aqueous aluminum brazing composition.
(2) The aqueous aluminum brazing composition according to (1), wherein the water-soluble polymer is polyvinyl alcohol.
(3) The aqueous aluminum brazing according to (1) or (2), wherein the content ratio of the fluoride flux to the binder is 99.5: 0.5 to 75:25 by mass ratio Composition.
(4) In any one of the items (1) to (3), the content ratio of the binder is 0.1 to 10% by mass in terms of solid content with respect to the total amount of the aqueous aluminum brazing composition. The composition for aqueous | water-based aluminum brazing of description.
(5) A brazing member obtained by applying the aqueous aluminum brazing composition according to any one of (1) to (4) to one or both surfaces of an aluminum substrate surface.
(6) The brazing member according to (5), wherein the coating amount of the aqueous aluminum brazing composition is 5 to 60 g as a dry mass per 1 m 2 of the aluminum substrate surface.
 本発明によれば、アルミニウムまたはアルミニウム合金製の部材に対するフラックスの密着性として良好な特性を得ることができる。さらに、分散媒中の水の割合を多くしてもフラックスを安定して分散させることができ、これにより、揮発性有機化合物の含有量が抑制された水系アルミニウムろう付用組成物を提供することができる。 According to the present invention, good characteristics can be obtained as the adhesiveness of the flux to the aluminum or aluminum alloy member. Furthermore, even if the proportion of water in the dispersion medium is increased, it is possible to stably disperse the flux, thereby providing an aqueous aluminum brazing composition in which the content of volatile organic compounds is suppressed. Can do.
ろう付性の評価サンプルを示す外観図である。It is an external view which shows the evaluation sample of brazing property. ろう付温度に加熱した後の評価用サンプルを模式的に示す側面図である。It is a side view which shows typically the sample for evaluation after heating to brazing temperature. スプレー密着性の評価方法を示す概略図である。It is the schematic which shows the evaluation method of spray adhesiveness.
 (水系アルミニウムろう付用組成物)
 本発明の水系アルミニウムろう付用組成物は、フッ化物系フラックスと、バインダと、分散媒とを含む。
(Water-based aluminum brazing composition)
The aqueous aluminum brazing composition of the present invention contains a fluoride flux, a binder, and a dispersion medium.
 本発明に用いられるフッ化物系フラックスは、ろう付時において、アルミニウム表面の酸化被膜を除去する。フッ化物系フラックスとしては、アルミニウムのろう付に用いられる各種のものが挙げられる。具体的には、例えば、フルオロアルミン酸カリウム、フッ化カリウム、フッ化アルミニウム、フッ化リチウム、フッ化ナトリウム、フルオロアルミン酸カリウム-セシウム錯体(非反応性セシウム系フラックス)、フルオロアルミン酸セシウム(非反応性セシウム系フラックス)、フルオロ亜鉛酸カリウム(反応性亜鉛置換フラックス)、フルオロ亜鉛酸セシウム(反応性亜鉛置換フラックス)などが挙げられる。フッ化物系フラックスは、例示の化合物を単独で用いてもよく、2種以上を併用してもよい。 Fluoride flux used in the present invention removes the oxide film on the aluminum surface during brazing. Examples of the fluoride-based flux include various types used for brazing aluminum. Specifically, for example, potassium fluoroaluminate, potassium fluoride, aluminum fluoride, lithium fluoride, sodium fluoride, potassium fluoroaluminate-cesium complex (non-reactive cesium-based flux), cesium fluoroaluminate (non-reactive) Reactive cesium flux), potassium fluorozincate (reactive zinc substitution flux), cesium fluorozincate (reactive zinc substitution flux), and the like. As the fluoride-based flux, the exemplified compounds may be used alone or in combination of two or more.
 市販されているフッ化物系フラックスとしては、例えば、ソルベイ(Solvay)社製の「ノコロック(Nocolok、登録商標)フラックス(フルオロアルミン酸カリウム)」、「ノコロック(登録商標)Silフラックス」(フルオロアルミン酸カリウムと金属ケイ素粉末との混合物)、「ノコロック(登録商標)Csフラックス(セシウム系フラックス)」などが挙げられる。 Commercially available fluoride fluxes include, for example, “Nocolok (registered trademark) flux (potassium fluoroaluminate)”, “Nocolok (registered trademark) Sil flux” (fluoroaluminate) manufactured by Solvay. A mixture of potassium and metal silicon powder), “Nocolok (registered trademark) Cs flux (cesium-based flux)” and the like.
 本発明に用いられるバインダは、水溶性ポリマーである。水溶性ポリマーの分子量は特に限定されない。しかし、従来のろう付用組成物において沈降防止剤として用いられるような低分子量のものではなく、ある程度高分子量のものが求められる。分子量がある程度大きい水溶性ポリマーを用いることで、アルミニウム製の部材に対するフラックスの密着性を良好にすることができる。具体的には、水溶性ポリマーの分子量は、GPC法による重量平均分子量で、50000~300000であることが好ましく、80000~200000であることがより好ましい。 The binder used in the present invention is a water-soluble polymer. The molecular weight of the water-soluble polymer is not particularly limited. However, a low molecular weight is required rather than a low molecular weight used as an anti-settling agent in conventional brazing compositions. By using a water-soluble polymer having a certain molecular weight, the adhesion of the flux to the aluminum member can be improved. Specifically, the molecular weight of the water-soluble polymer is preferably 50,000 to 300,000, more preferably 80000 to 200,000, as a weight average molecular weight according to the GPC method.
 水溶性ポリマーとしては、例えば、ポリビニルアルコール、ポリエチレンオキサイド、水系ポリエステル樹脂、メチルセルロース、水系エポキシ樹脂などが挙げられる。これらの水溶性ポリマーは、熱分解性に優れているため、ろう付時に揮発しやすく、炭化物の残渣が残りにくい。特に、本発明に用いられるバインダとしては、ポリビニルアルコールが好ましい。バインダは、単独で用いてもよく、2種以上を併用してもよい。 Examples of the water-soluble polymer include polyvinyl alcohol, polyethylene oxide, water-based polyester resin, methyl cellulose, water-based epoxy resin, and the like. Since these water-soluble polymers are excellent in thermal decomposability, they tend to volatilize during brazing, and carbide residues are unlikely to remain. In particular, polyvinyl alcohol is preferable as the binder used in the present invention. A binder may be used independently and may use 2 or more types together.
 本発明に用いられる分散媒は、水単独または水とVOCとの混合物が挙げられる。特に、分散媒として水を単独で用いることが好ましい。分散媒が、水とVOCとの混合物である場合において、分散媒中に含まれるVOCの量は、水系アルミニウムろう付用組成物の総量に対して10質量%以下となるように設定される。VOCの含有割合が水系アルミニウムろう付用組成物の総量に対して10質量%以下であるならば、従来のアルミニウムろう付用組成物と比べて、十分に「低VOC」の組成物であるということができる。水系アルミニウムろう付用組成物の総量に対するVOCの含有割合は、特に5質量%以下であることがより好ましい。 The dispersion medium used in the present invention includes water alone or a mixture of water and VOC. In particular, it is preferable to use water alone as a dispersion medium. When the dispersion medium is a mixture of water and VOC, the amount of VOC contained in the dispersion medium is set to be 10% by mass or less based on the total amount of the aqueous aluminum brazing composition. If the content of VOC is 10% by mass or less with respect to the total amount of the aqueous aluminum brazing composition, the composition is sufficiently “low VOC” compared to the conventional aluminum brazing composition. be able to. The content ratio of VOC with respect to the total amount of the aqueous aluminum brazing composition is more preferably 5% by mass or less.
 VOCとしては特に限定されないが、水との相溶性が高いものが好ましい。具体的には、メタノール、エタノール、n-プロピルアルコール、イソプロピルアルコール、1,3-ブタンジオール、3-メチル-1,3-ブタンジオール、3-メトキシ-3-メチル-1-ブタノール(MMB)などのアルコール類;アセトン、メチルエチルケトン、イソブチルケトンなどのケトン類;ジエチルエーテルなどのエーテル類;ナフテン系脂環式炭化水素類;エチレングリコールメチルエーテル、エチレングリコールエチルエーテル、エチレングリコールブチルエーテル、ジエチレングリコールメチルエーテル、ジエチレングリコールエチルエーテル、ジエチレングリコールブチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノブチルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノエチルエーテル、ジプロピレングリコールモノブチルエーテルなどのグリコールエーテル類、などが挙げられる。 Although it does not specifically limit as VOC, A thing with high compatibility with water is preferable. Specifically, methanol, ethanol, n-propyl alcohol, isopropyl alcohol, 1,3-butanediol, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol (MMB), etc. Alcohols such as acetone, methyl ethyl ketone, isobutyl ketone, etc .; ethers such as diethyl ether; naphthenic alicyclic hydrocarbons; ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol butyl ether, diethylene glycol methyl ether, diethylene glycol Ethyl ether, diethylene glycol butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether Dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, glycol ethers such as dipropylene glycol monobutyl ether, and the like.
 上記フッ化物系フラックス、バインダ、および分散媒の配合量は、水系アルミニウムろう付用組成物としての機能を発揮し得る範囲であれば特に限定されない。例えば、フッ化物系フラックスの配合量は、バインダの配合量にもよるが、水系アルミニウムろう付用組成物の総量に対して5~50質量%が好ましく、10~40質量%がより好ましい。フッ化物系フラックスの配合量が少ない場合には、ろう付時に塗布される水系アルミニウムろう付用組成物の量が過大になる傾向がある。フッ化物系フラックスの配合量が多い場合には、水系アルミニウムろう付用組成物の粘度が高くなる傾向があり、バインダの配合量によって、アルミニウム製部材の表面にフッ化物系フラックスを付着させる効果が低下するおそれがある。 The blending amount of the fluoride flux, binder, and dispersion medium is not particularly limited as long as it can function as a water-based aluminum brazing composition. For example, the blending amount of the fluoride-based flux is preferably 5 to 50% by weight, more preferably 10 to 40% by weight, based on the total amount of the aqueous aluminum brazing composition, although it depends on the blending amount of the binder. When the blending amount of the fluoride-based flux is small, the amount of the aqueous aluminum brazing composition applied during brazing tends to be excessive. When the amount of fluoride-based flux is large, the viscosity of the water-based aluminum brazing composition tends to be high, and the effect of attaching the fluoride-based flux to the surface of the aluminum member depends on the amount of binder. May decrease.
 バインダの配合量は、フッ化物系フラックスの配合量にもよるが、水系アルミニウムろう付用組成物の総量に対して0.1~10質量%が好ましく、0.3~4質量%がより好ましい。バインダの配合量が少ない場合には、フッ化物系フラックスの配合量によって、アルミニウム製部材の表面にフッ化物系フラックスを付着させる効果が低下するおそれがある。バインダの配合量が多い場合には、水系アルミニウムろう付用組成物の粘度が高くなる傾向がある。 The amount of the binder is preferably 0.1 to 10% by mass, more preferably 0.3 to 4% by mass, based on the total amount of the aqueous aluminum brazing composition, although it depends on the amount of fluoride flux. . When the blending amount of the binder is small, the effect of attaching the fluoride flux to the surface of the aluminum member may be reduced depending on the blending amount of the fluoride flux. When the amount of the binder is large, the viscosity of the aqueous aluminum brazing composition tends to increase.
 フッ化物系フラックスとバインダとの質量比は、特に限定されないが、99.5:0.5~75:25が好ましく、99:1~80:20がより好ましく、99:1~90:10が特に好ましい。フッ化物系フラックスとバインダとを、このような質量比で含有することにより、ろう付性と粘着性とのバランスをとることができる。 The mass ratio between the fluoride-based flux and the binder is not particularly limited, but is preferably 99.5: 0.5 to 75:25, more preferably 99: 1 to 80:20, and 99: 1 to 90:10. Particularly preferred. By containing the fluoride-based flux and the binder in such a mass ratio, it is possible to balance the brazing property and the adhesiveness.
 本発明の水系アルミニウムろう付用組成物には、本発明の効果を阻害しない範囲で、必要に応じて他の添加剤を配合することができる。他の添加剤としては、例えば、ジブチルヒドロキシトルエン(BHT)などの酸化防止剤;ベンゾトリアゾールなどの腐食防止剤;シリコンオイル、グリセリンなどの消泡剤;ワックス、硬化油、脂肪酸アミド、ポリアミドなどの増粘剤;着色剤などが挙げられる。 The water-based aluminum brazing composition of the present invention can be blended with other additives as necessary within a range that does not impair the effects of the present invention. Other additives include, for example, antioxidants such as dibutylhydroxytoluene (BHT); corrosion inhibitors such as benzotriazole; antifoaming agents such as silicone oil and glycerin; waxes, hardened oils, fatty acid amides, polyamides and the like Thickeners; coloring agents and the like.
 本発明の水系アルミニウムろう付用組成物は、例えば、高温に加熱された被着物に対してスプレー塗布される。このようにスプレー塗布することによって、水系アルミニウムろう付用組成物に含まれる分散媒が一気に揮散し、フラックスおよびバインダの塗膜がろう接部分に形成される。また、本発明の水系アルミニウムろう付用組成物は、後述するろう付用部材の材料としても用いられる。 The aqueous aluminum brazing composition of the present invention is spray-applied to an adherend heated to a high temperature, for example. By spray coating in this way, the dispersion medium contained in the aqueous aluminum brazing composition is volatilized at once, and a coating film of flux and binder is formed on the brazed portion. Moreover, the composition for water-system aluminum brazing of this invention is used also as a material of the member for brazing mentioned later.
 (ろう付用部材)
 本発明の水系アルミニウムろう付用組成物は、例えば、アルミニウムの基材表面に塗布し、乾燥させた状態で、ろう付用部材として供給することができる。
(Brass material)
The aqueous aluminum brazing composition of the present invention can be supplied, for example, as a brazing member in a state where it is applied to the surface of an aluminum substrate and dried.
 基材は、アルミニウムまたはアルミニウム合金製であり、その厚みは特に限定されず、所望の用途(形成品)に応じて適宜設定することができる。また、基材の表面には、ろう材が塗布される。ろう材としては、金属ケイ素、ケイ素-アルミニウム合金、これらに少量のマグネシウム、銅、ゲルマニウムなどを含む合金などが挙げられる。 The base material is made of aluminum or an aluminum alloy, and the thickness thereof is not particularly limited, and can be appropriately set according to a desired application (formed product). A brazing material is applied to the surface of the substrate. Examples of the brazing material include metallic silicon, silicon-aluminum alloys, alloys containing a small amount of magnesium, copper, germanium, and the like.
 次いで、水系アルミニウムろう付用組成物が基材に塗布される。塗布方法は、例えば、スプレー法、ロールコート法、浸漬法などから適宜選択できるが、スプレー法が特に好ましい。 Next, the aqueous aluminum brazing composition is applied to the substrate. The coating method can be appropriately selected from, for example, a spray method, a roll coating method, a dipping method, and the like, but the spray method is particularly preferable.
 水系アルミニウムろう付用組成物の塗布量は、ろう付性と塗布安定性との観点から、塗布面1m2あたりの乾燥質量として、好ましくは5~60g、より好ましくは10~40gである。なお、水系アルミニウムろう付用組成物がろう材を含む場合は、上記ろう材の塗布量と水系アルミニウムろう付用組成物の塗布量との合計量を塗布すればよい。 The coating amount of the aqueous aluminum brazing composition is preferably 5 to 60 g, more preferably 10 to 40 g as a dry mass per 1 m 2 of the coated surface from the viewpoints of brazing and coating stability. In addition, what is necessary is just to apply | coat the total amount of the application quantity of the said brazing material and the application quantity of the composition for aqueous | water-based aluminum brazing, when the composition for aqueous | water-based aluminum brazing contains a brazing material.
 ろう材や水系アルミニウムろう付用組成物は、用途に応じて、基材表面の片面のみに塗布してもよく、両面に塗布してもよい。また、基材がある程度の厚みを有する場合は、側面に塗布してもよい。 The brazing material and the aqueous aluminum brazing composition may be applied to only one surface of the base material surface or may be applied to both surfaces depending on the application. Moreover, when a base material has a certain amount of thickness, you may apply | coat to a side surface.
 本発明の水系アルミニウムろう付用組成物やろう付用部材は、車両に搭載されるエバポレータ、コンデンサなど自動車用熱交換器などの材料として用いられ、得られる形成品(自動車用熱交換器など)の外観は、ろう付不良や塗膜にひび割れなどが存在せず、良好である。 The water-based aluminum brazing composition or brazing member of the present invention is used as a material for an automotive heat exchanger such as an evaporator or a capacitor mounted on a vehicle, and a molded product obtained (such as an automotive heat exchanger). The appearance of this is good with no brazing defects or cracks in the coating film.
 以下、実施例および比較例を挙げて本発明を具体的に説明するが、本発明はこれらの実施例に限定されるものではない。 Hereinafter, the present invention will be specifically described with reference to examples and comparative examples, but the present invention is not limited to these examples.
 <水系アルミニウムろう付用組成物の調製>
 以下の実施例および比較例において、フラックスとしては、ソルベイ社製の「ノコロック(登録商標)Silフラックス」(フルオロアルミン酸カリウムと金属ケイ素粉末との混合物)を用いた。バインダとしては、日本酢ビ・ポバール株式会社製のポリビニルアルコール(PVA、品番JF-20、重量平均分子量15万)を用いた。重量平均分子量は、ビスコテック社(Viscotek Corp.)製のゲル浸透クロマトグラフ(GPC)、型番TDA-302を用いて、GPC法により測定した。また、分散媒としては、水単独、または水とVOC(3-メトキシ-3-メチル-1-ブタノール(MMB))との混合溶媒を用いた。
<Preparation of aqueous aluminum brazing composition>
In the following examples and comparative examples, “Nocolok (registered trademark) Sil flux” (mixture of potassium fluoroaluminate and metal silicon powder) manufactured by Solvay was used as the flux. As a binder, polyvinyl alcohol (PVA, product number JF-20, weight average molecular weight 150,000) manufactured by Nippon Vinegar Pover Co., Ltd. was used. The weight average molecular weight was measured by a GPC method using a gel permeation chromatograph (GPC) manufactured by Viscotek Corp., model number TDA-302. As the dispersion medium, water alone or a mixed solvent of water and VOC (3-methoxy-3-methyl-1-butanol (MMB)) was used.
 (実施例1)
 フラックスとPVAとを水に加えて、攪拌することにより、水系アルミニウムろう付用組成物を得た。組成物の全量に対する各成分の含有割合は、表1に示すように、フラックスが5質量%、PVAが0.4質量%および残量が水であり、フラックスとバインダ(PVA)との質量比は92.6:7.4であった。
Example 1
Flux and PVA were added to water and stirred to obtain an aqueous aluminum brazing composition. As shown in Table 1, the content ratio of each component with respect to the total amount of the composition is such that the flux is 5% by mass, the PVA is 0.4% by mass, the remaining amount is water, and the mass ratio of the flux to the binder (PVA) Was 92.6: 7.4.
 (実施例2~10および12~17)
 フラックスおよびPVAの含有割合を表1に示すように設定したこと以外は、実施例1と同様にして水系アルミニウムろう付用組成物を得た。
(Examples 2 to 10 and 12 to 17)
An aqueous aluminum brazing composition was obtained in the same manner as in Example 1 except that the content ratios of the flux and PVA were set as shown in Table 1.
  (実施例11)
 フラックスとPVAとを、水およびMMBの混合分散媒中に加えて、攪拌することにより、水系アルミニウムろう付用組成物を得た。組成物の全量に対する各成分の含有割合は、表1に示すように、フラックスが30質量%、PVAが2.2質量%、MMBが10質量%および残量が水であり、フラックスとPVAとの質量比は93.2:6.8であった。
(Example 11)
A flux and PVA were added to a mixed dispersion medium of water and MMB, and the mixture was stirred to obtain an aqueous aluminum brazing composition. As shown in Table 1, the content ratio of each component with respect to the total amount of the composition is 30% by mass of flux, 2.2% by mass of PVA, 10% by mass of MMB, and the remaining amount of water. The mass ratio was 93.2: 6.8.
 (比較例1~3)
 フラックス、PVA、水およびMMBの含有割合を表1に示すように設定したこと以外は、実施例11と同様にして水系アルミニウムろう付用組成物を得た。
(Comparative Examples 1 to 3)
An aqueous aluminum brazing composition was obtained in the same manner as in Example 11 except that the content ratios of flux, PVA, water and MMB were set as shown in Table 1.
 (参考例1)
 <アクリル樹脂の合成>
 従来用いられているアクリル系バインダを、次のように合成した。撹拌装置、冷却管、滴下ロートおよび窒素導入管を備えた反応装置に、600質量部のイソプロピルアルコールを仕込み、窒素気流下で系内温度が80℃となるまで昇温した。次いで、100質量部のメタクリル酸メチル、275質量部のメタクリル酸イソブチル、25質量部のメタクリル酸および4質量部の過酸化ベンゾイルを含む混合溶液を約3時間かけて系内に滴下した。滴下終了後、さらに10時間、反応温度を80℃に保って重合を完結させ、樹脂溶液を得た。
(Reference Example 1)
<Synthesis of acrylic resin>
A conventionally used acrylic binder was synthesized as follows. A reactor equipped with a stirrer, a cooling tube, a dropping funnel and a nitrogen introducing tube was charged with 600 parts by mass of isopropyl alcohol, and the system temperature was raised to 80 ° C. under a nitrogen stream. Subsequently, a mixed solution containing 100 parts by mass of methyl methacrylate, 275 parts by mass of isobutyl methacrylate, 25 parts by mass of methacrylic acid and 4 parts by mass of benzoyl peroxide was dropped into the system over about 3 hours. After completion of the dropwise addition, the reaction temperature was kept at 80 ° C. for 10 hours to complete the polymerization to obtain a resin solution.
 次いで、撹拌装置、蒸気凝集除去装置および窒素導入管を備えた反応装置に、750質量部の上記樹脂溶液、700質量部のイオン交換水および18質量部のジメチルアミノエタノールを仕込み、窒素気流下で系内が還流するまで昇温した。蒸気凝集除去装置を用いて、系内のイソプロピルアルコール450質量部を除去し、アルミニウムろう付け用バインダ(固形分:30質量%)を得た。なお、従来用いられているこのアクリル系バインダを用いてろう付用組成物を調製する場合は、当該アクリル系バインダの水溶媒中での溶解性が低いため、VOCの含有量を多くして、安定化を図っていた。 Subsequently, 750 parts by mass of the resin solution, 700 parts by mass of ion-exchanged water and 18 parts by mass of dimethylaminoethanol were charged into a reactor equipped with a stirrer, a vapor agglomeration and removal unit, and a nitrogen introduction tube, and under a nitrogen stream. The temperature was raised until the system was refluxed. Using a vapor agglomeration removal apparatus, 450 parts by mass of isopropyl alcohol in the system was removed to obtain an aluminum brazing binder (solid content: 30% by mass). In addition, when preparing a brazing composition using this acrylic binder that has been conventionally used, since the solubility of the acrylic binder in an aqueous solvent is low, the content of VOC is increased, Stabilization was planned.
 <ろう付用組成物の調製>
 上述のアクリル樹脂と、フラックスとを、水およびMMBの混合分散媒中に加えて、攪拌することにより、アルミニウムろう付用組成物を得た。フラックスは、実施例1で用いたものと同じものを用いた。組成物の全量に対する各成分の含有割合は、表1に示すように、フラックスが30質量%、アクリル樹脂が3質量%、MMBが3質量%および残量が水であり、フラックスとバインダ(アクリル樹脂)との質量比は90.9:9.1であった。
<Preparation of brazing composition>
The above-mentioned acrylic resin and flux were added to a mixed dispersion medium of water and MMB and stirred to obtain an aluminum brazing composition. The same flux as that used in Example 1 was used. As shown in Table 1, the content ratio of each component with respect to the total amount of the composition is as follows: the flux is 30% by mass, the acrylic resin is 3% by mass, the MMB is 3% by mass, the remaining amount is water, and the flux and binder (acrylic) The mass ratio with respect to (resin) was 90.9: 9.1.
 (参考例2)
 上述のアクリル樹脂、フラックス、水、およびMMBの含有割合を表1に示すように設定したこと以外は、参考例1と同様にしてアルミニウムろう付用組成物を得た。
(Reference Example 2)
An aluminum brazing composition was obtained in the same manner as in Reference Example 1, except that the contents of the acrylic resin, flux, water, and MMB were set as shown in Table 1.
 (参考例3)
 表1に示すように、フラックスを5質量%、PVAを0.1質量%、MMBを20質量%および残量を水としたこと以外は、実施例11と同様にして水系アルミニウムろう付用組成物を得た。なお、フラックスとPVAとの質量比は98:2であった。
(Reference Example 3)
As shown in Table 1, an aqueous aluminum brazing composition was used in the same manner as in Example 11 except that the flux was 5% by mass, PVA was 0.1% by mass, MMB was 20% by mass, and the remaining amount was water. I got a thing. The mass ratio of flux to PVA was 98: 2.
 <アルミニウムろう付用組成物の評価>
 上記実施例、比較例および参考例で得られたアルミニウムろう付用組成物を用いて、下記(1)~(5)の測定および評価を行った。結果を表2に示す。
<Evaluation of composition for aluminum brazing>
Using the aluminum brazing compositions obtained in the above examples, comparative examples and reference examples, the following measurements (1) to (5) were carried out and evaluated. The results are shown in Table 2.
 (1)ろう付性
 ろう付性の評価サンプルの外観図を図1に示し、ろう付温度に加熱した後の評価サンプルの側面図を図2に示す。
(1) Brazeability FIG. 1 shows an external view of a brazeability evaluation sample, and FIG. 2 shows a side view of the evaluation sample after heating to a brazing temperature.
 <評価サンプルの作製>
 まず、図1を参照して、ろう付性の評価サンプル10の作製工程を説明する。ろう付性の評価サンプル10は、幅W1およびW2が25mm、長さL1およびL2が70mm、厚さが2.0mm(アルミニウム平板11)と0.8mm(アルミニウム平板12)である2枚のアルミニウム平板11、12と、直径1.6mmのステンレス線13とを備える。第1のアルミニウム平板11には、上面にろう材面となるアルミニウム-ケイ素系合金(JIS-A4047P、0.2mm)を、下面に心材となる純アルミニウム(JIS-A1050P、1.8mm)を圧延した平板を用いた。第2のアルミニウム平板12には、純アルミニウム(JIS-A1050P)製の平板を用いた。
<Preparation of evaluation sample>
First, with reference to FIG. 1, the manufacturing process of the brazeability evaluation sample 10 will be described. The brazeability evaluation sample 10 has a width W 1 and W 2 of 25 mm, a length L 1 and L 2 of 70 mm, and a thickness of 2.0 mm (aluminum flat plate 11) and 0.8 mm (aluminum flat plate 12). Two aluminum flat plates 11 and 12 and a stainless steel wire 13 having a diameter of 1.6 mm are provided. The first aluminum flat plate 11 is rolled with an aluminum-silicon alloy (JIS-A4047P, 0.2 mm) serving as a brazing material surface on the upper surface and pure aluminum (JIS-A1050P, 1.8 mm) serving as a core material on the lower surface. A flat plate was used. As the second aluminum flat plate 12, a flat plate made of pure aluminum (JIS-A1050P) was used.
 第1のアルミニウム平板11を200℃に加熱して、ろう材表面にアルミニウムろう付用組成物を塗布することにより、表面に塗布層を形成した。アルミニウムろう付用組成物としては、上述の実施例、比較例および参考例で作成したものを用いた。 The first aluminum flat plate 11 was heated to 200 ° C., and an aluminum brazing composition was applied to the surface of the brazing material to form a coating layer on the surface. As the aluminum brazing composition, those prepared in the above-mentioned Examples, Comparative Examples and Reference Examples were used.
 次に、第2のアルミニウム平板12の長辺側における一の端縁E1を、第1のアルミニウム平板11の表面(ろう材面)14に対して突き合わせて、端縁E1が第1のアルミニウム平板11の長さ方向L1に沿うように配置した。この時、第2のアルミニウム平板12における端縁E1の一の角部C1を、第1のアルミニウム平板11の表面14に接触させた。また、端縁E1の他の角部C2側を、第1のアルミニウム平板11の表面14に配置されたステンレス線13と接触させた。このようにステンレス線13を挟むことにより、第1のアルミニウム平板11の表面14と第2のアルミニウム平板12の端縁E1との間には、一の角部C1から他の角部C2にかけて間隔が広がる楔形の隙間が形成された。第2のアルミニウム平板12の角部C1側から、第1のアルミニウム平板11とステンレス線13との接線までの距離Dを45mmに設定し、第1のアルミニウム平板11と第2のアルミニウム平板12とを図示しないワイヤーで固定した。 Next, one end edge E 1 on the long side of the second aluminum flat plate 12 is abutted against the surface (brazing material surface) 14 of the first aluminum flat plate 11 so that the end edge E 1 is the first end. It was placed along the length L 1 of the aluminum flat plate 11. At this time, one corner C 1 of the edge E 1 of the second aluminum flat plate 12 was brought into contact with the surface 14 of the first aluminum flat plate 11. Further, the other corner C 2 side of the edge E 1 was brought into contact with the stainless steel wire 13 disposed on the surface 14 of the first aluminum flat plate 11. By sandwiching the stainless steel wire 13 in this way, between the surface 14 of the first aluminum flat plate 11 and the edge E 1 of the second aluminum flat plate 12 from one corner C 1 to another corner C A wedge-shaped gap was formed with a gap extending to 2 . The distance D from the corner C 1 side of the second aluminum flat plate 12 to the tangent line between the first aluminum flat plate 11 and the stainless steel wire 13 is set to 45 mm, and the first aluminum flat plate 11 and the second aluminum flat plate 12 are set. Were fixed with a wire (not shown).
 <ろう付性の評価>
 上記評価サンプル10をろう付温度である600℃に加熱して、第1のアルミニウム平板11と第2のアルミニウム平板12とをろう付した。ろう付性の評価は、ろう付後におけるろう材の充填長さL3(図2参照)が大きいほど良好である。なお、充填長さL3の最大値は、上述の距離Dに相当する45mmである。
<Evaluation of brazing>
The said evaluation sample 10 was heated to 600 degreeC which is brazing temperature, and the 1st aluminum flat plate 11 and the 2nd aluminum flat plate 12 were brazed. The evaluation of the brazing property is better as the filling length L 3 (see FIG. 2) of the brazing material after brazing is larger. The maximum value of the filling length L 3 is 45 mm corresponding to the distance D described above.
 ろう付性の評価基準は下記のとおりである。
A:充填長さL3が40mm以上で、ろう付性が極めて良好な場合。
B:充填長さL3が20mm以上40mm未満で、実用上許容できるろう付性が得られる場合。
C:充填長さL3が20mm未満で、ろう付性が不十分な場合。
The evaluation criteria for brazeability are as follows.
A: When the filling length L 3 is 40 mm or more and the brazing property is very good.
B: When the filling length L 3 is 20 mm or more and less than 40 mm and brazing properties that are practically acceptable are obtained.
C: When the filling length L 3 is less than 20 mm and the brazability is insufficient.
 (2)密着性
 密着性の評価方法を示す概略図を図3に示す。
(2) Adhesiveness FIG. 3 is a schematic diagram showing an evaluation method for adhesiveness.
 <評価用サンプルの作製>
 図3を参照して、スプレー密着性の評価用サンプル20は、アルミニウム平板21と、その一方の表面に形成された塗布層22と、を備える。アルミニウム平板21には、長さ150mm、幅70mmの純アルミニウム(JIS-A1050P)製の平板を用いた。塗布層22は、予め200℃に加熱されたアルミニウム平板21の表面に、アルミニウムろう付組成物をスプレー塗布して、加熱により分散媒を除去することにより形成した。アルミニウムろう付用組成物としては、上記実施例、比較例、および参考例で作成したものを用い、その塗布量は15g/m2に設定した。
<Preparation of sample for evaluation>
With reference to FIG. 3, the sample 20 for spray adhesion evaluation includes an aluminum flat plate 21 and a coating layer 22 formed on one surface thereof. As the aluminum flat plate 21, a flat plate made of pure aluminum (JIS-A1050P) having a length of 150 mm and a width of 70 mm was used. The coating layer 22 was formed by spray-coating the aluminum brazing composition on the surface of the aluminum flat plate 21 previously heated to 200 ° C. and removing the dispersion medium by heating. As the aluminum brazing composition, those prepared in the above Examples, Comparative Examples and Reference Examples were used, and the coating amount was set to 15 g / m 2 .
 <密着性の評価>
 塗布層22が形成されたアルミニウム平板21を、塗布層22を上に向けて平台上に設置した。塗布層22の表面にプラスチック製の字消し23(三菱鉛筆株式会社製の「uniプラスチック字消し」)を載せて、鉛直方向に1kgf(9.8N)の荷重をかけながら、アルミニウム平板21の表面を一方向に往復させた。こうして、プラスチック字消しの摩擦によって塗布層22が完全に削られたときの往復回数(以下、単に「往復回数」という)をカウントした。密着性は、往復回数が多いほど良好である。
<Evaluation of adhesion>
The aluminum flat plate 21 on which the coating layer 22 was formed was placed on a flat table with the coating layer 22 facing upward. The surface of the aluminum flat plate 21 is placed on the surface of the coating layer 22 while placing a plastic eraser 23 ("uni plastic eraser" manufactured by Mitsubishi Pencil Co., Ltd.) and applying a load of 1 kgf (9.8 N) in the vertical direction. Was reciprocated in one direction. Thus, the number of reciprocations when the coating layer 22 was completely scraped by the plastic eraser friction (hereinafter simply referred to as “the number of reciprocations”) was counted. The adhesion is better as the number of reciprocations is larger.
 密着性の評価基準は下記のとおりである。
A+:往復回数が10回以上で、密着性が極めて良好な場合。
A:往復回数が4回以上10回未満で、密着性が良好な場合。
B:往復回数が2回以上4回未満で、実用上許容できる密着性が得られる場合。
C:往復回数が2回未満で、密着性が不十分な場合。
The evaluation criteria for adhesion are as follows.
A +: When the number of reciprocations is 10 times or more and the adhesion is very good.
A: The number of reciprocations is 4 times or more and less than 10 times, and the adhesion is good.
B: The number of reciprocations is 2 times or more and less than 4 times, and practically acceptable adhesion can be obtained.
C: When the number of reciprocations is less than 2 and adhesion is insufficient.
 (3)粘度
 上記実施例、比較例、および参考例の各アルミニウムろう付用組成物について、E型粘度計(東機産業株式会社製の型番「TV-22」)を用いて粘度を測定することにより、スプレー塗布に適しているか否かを評価した。測定条件は、測定温度を25℃とし、測定サンプルの回転速度を100回転/分とした。
(3) Viscosity For each of the compositions for aluminum brazing in the above Examples, Comparative Examples, and Reference Examples, the viscosity is measured using an E-type viscometer (model number “TV-22” manufactured by Toki Sangyo Co., Ltd.). Thus, it was evaluated whether it was suitable for spray application. The measurement conditions were a measurement temperature of 25 ° C. and a rotation speed of the measurement sample of 100 rotations / minute.
 粘度の測定結果とスプレー塗布への使用の可否の判断基準は、下記のとおりである。
A:粘度が200mPa・s-1以下であって、スプレー塗布に極めて適している場合。
B:粘度が200mPa・s-1を超え500mPa・s-1以下であって、スプレー塗布への適用に実用上許容できる範囲である場合。
C:粘度が500mPa・s-1を超えるスプレー塗布に適していない場合。
The measurement results of the viscosity and the criteria for determining whether or not to use for spray coating are as follows.
A: When the viscosity is 200 mPa · s −1 or less and is extremely suitable for spray coating.
B: When the viscosity is more than 200 mPa · s −1 and 500 mPa · s −1 or less and is practically acceptable for application to spray coating.
C: When the viscosity is not suitable for spray coating exceeding 500 mPa · s −1 .
 (4)低VOC性
 VOCの含有量の程度を下記の段階でランク分けした。
A:VOCの含有割合が5質量%以下であって、低VOC性が極めて良好な場合。
B:VOCの含有割合が5質量%を超え10質量%以下で良好な場合。
C:VOCの含有割合が10質量%を超え、VOC量の低減が不十分な場合。
(4) Low VOC property The degree of VOC content was ranked in the following stages.
A: When the content ratio of VOC is 5% by mass or less and the low VOC property is very good.
B: When the content ratio of VOC exceeds 5% by mass and is 10% by mass or less.
C: The content ratio of VOC exceeds 10% by mass, and the amount of VOC is not sufficiently reduced.
 (5)安定性
 上記実施例、比較例および参考例のアルミニウムろう付用組成物各2kgを、40℃の環境下で30日間保管した後、40メッシュ(目開き0.35mm)のろ過フィルタを用いてろ過した。次いで、ろ過フィルタを乾燥させて、ろ過フィルタ上の残渣の質量を測定した。アルミニウムろう付用組成物の全量に対する残渣の質量割合が小さいほど、安定性が良好である。
(5) Stability After storing 2 kg of each of the compositions for aluminum brazing in the above Examples, Comparative Examples and Reference Examples for 30 days in an environment of 40 ° C., a 40 mesh (aperture 0.35 mm) filtration filter was used. And filtered. Subsequently, the filtration filter was dried and the mass of the residue on the filtration filter was measured. The smaller the mass ratio of the residue to the total amount of the aluminum brazing composition, the better the stability.
 安定性は、下記の基準により評価した。
A:残渣の割合が0.05質量%以下であり、安定性が極めて良好な場合。
B:残渣の割合が0.05質量%を超え0.2質量%以下であって、実用上許容できる安定性が得られる場合。
C:残渣の割合が0.2質量%を超え安定性が不十分な場合。
Stability was evaluated according to the following criteria.
A: When the ratio of the residue is 0.05% by mass or less and the stability is very good.
B: The proportion of the residue is more than 0.05% by mass and 0.2% by mass or less, and practically acceptable stability is obtained.
C: The ratio of the residue exceeds 0.2% by mass and the stability is insufficient.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
 表2に示すように、本発明の組成物(実施例1~17)は、ろう付性、密着性、粘度、低VOC性および安定性のいずれも良好であることがわかる。一方、比較例1~3の組成物は、VOCの含有量が多く、ろう付性、密着性および粘度のいずれかに劣ることがわかる。 As shown in Table 2, it can be seen that the compositions of the present invention (Examples 1 to 17) are all good in brazeability, adhesion, viscosity, low VOC property and stability. On the other hand, it can be seen that the compositions of Comparative Examples 1 to 3 have a high VOC content and are inferior in any of brazing, adhesion, and viscosity.

Claims (6)

  1.  フッ化物系フラックスと、バインダと、分散媒とを含む水系アルミニウムろう付用組成物であって、
     前記バインダが水溶性ポリマーであり、
     前記分散媒が水または水と揮発性有機化合物との混合物であり、
     前記混合物中の揮発性有機化合物の含有量が、水系アルミニウムろう付用組成物総量に対して10質量%以下である、
    水系アルミニウムろう付用組成物。
    An aqueous aluminum brazing composition comprising a fluoride flux, a binder, and a dispersion medium,
    The binder is a water-soluble polymer;
    The dispersion medium is water or a mixture of water and a volatile organic compound;
    The content of the volatile organic compound in the mixture is 10% by mass or less based on the total amount of the aqueous aluminum brazing composition.
    An aqueous aluminum brazing composition.
  2.  前記水溶性ポリマーが、ポリビニルアルコールである、請求項1に記載の水系アルミニウムろう付用組成物。 The water-based aluminum brazing composition according to claim 1, wherein the water-soluble polymer is polyvinyl alcohol.
  3.  前記フッ化物系フラックスと前記バインダとの含有量の比が、質量比で99.5:0.5~75:25である、請求項1または2に記載の水系アルミニウムろう付用組成物。 3. The aqueous aluminum brazing composition according to claim 1 or 2, wherein the content ratio of the fluoride-based flux and the binder is 99.5: 0.5 to 75:25 in terms of mass ratio.
  4.  前記バインダの含有割合が、固形分換算で、水系アルミニウムろう付用組成物の総量に対して0.1~10質量%である、請求項1~3のいずれかの項に記載の水系アルミニウムろう付用組成物。 The aqueous aluminum brazing according to any one of claims 1 to 3, wherein a content of the binder is 0.1 to 10% by mass in terms of solid content with respect to a total amount of the aqueous aluminum brazing composition. Attached composition.
  5.  請求項1~4のいずれかの項に記載の水系アルミニウムろう付用組成物を、アルミニウムの基材表面の片面または両面に塗布して得られる、ろう付用部材。 A brazing member obtained by applying the aqueous aluminum brazing composition according to any one of claims 1 to 4 to one or both surfaces of an aluminum base material.
  6.  前記水系アルミニウムろう付用組成物の塗布量が、前記アルミニウムの基材表面1m2あたり、乾燥質量として5~60gである、請求項5に記載のろう付用部材。 The brazing member according to claim 5, wherein the coating amount of the aqueous aluminum brazing composition is 5 to 60 g as a dry mass per 1 m 2 of the aluminum substrate surface.
PCT/JP2012/074741 2011-09-30 2012-09-26 Aqueous composition for aluminum brazing WO2013047602A1 (en)

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Citations (6)

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Publication number Priority date Publication date Assignee Title
JPH07185796A (en) * 1993-12-27 1995-07-25 Nippondenso Co Ltd Brazing method
JPH10193086A (en) * 1997-01-16 1998-07-28 Nippon Light Metal Co Ltd Manufacture of aluminum heat exchanger, and aluminum heat exchanger
JP2005524534A (en) * 2001-05-02 2005-08-18 ノルスク・ヒドロ・アーエスアー The process of creating an article
JP2007175746A (en) * 2005-12-28 2007-07-12 Arakawa Chem Ind Co Ltd Binder for brazing aluminum and aqueous composition for brazing aluminum
JP2007521139A (en) * 2003-12-17 2007-08-02 ゾルファイ フルーオル ゲゼルシャフト ミット ベシュレンクテル ハフツング Flux
JP2009274087A (en) * 2008-05-13 2009-11-26 Calsonic Kansei Corp Method for stabilizing viscosity in stirred mixture of flux powder and binder

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07185796A (en) * 1993-12-27 1995-07-25 Nippondenso Co Ltd Brazing method
JPH10193086A (en) * 1997-01-16 1998-07-28 Nippon Light Metal Co Ltd Manufacture of aluminum heat exchanger, and aluminum heat exchanger
JP2005524534A (en) * 2001-05-02 2005-08-18 ノルスク・ヒドロ・アーエスアー The process of creating an article
JP2007521139A (en) * 2003-12-17 2007-08-02 ゾルファイ フルーオル ゲゼルシャフト ミット ベシュレンクテル ハフツング Flux
JP2007175746A (en) * 2005-12-28 2007-07-12 Arakawa Chem Ind Co Ltd Binder for brazing aluminum and aqueous composition for brazing aluminum
JP2009274087A (en) * 2008-05-13 2009-11-26 Calsonic Kansei Corp Method for stabilizing viscosity in stirred mixture of flux powder and binder

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