JP5555034B2 - Metal material-metal material joining paint, metal material obtained by using the same, metal material-coated metal material for joining metal material, and metal material-metal material joining method using the same - Google Patents

Description

  The present invention relates to a metal material-metal material bonding paint, a metal material-metal material-coated metal material obtained by using the same, and a metal material-metal material bonding method using the same. In order to join metal materials to each other, a paint applied to the joint surface of the metal material, a coated product made of a metal material to which such a paint is applied, and two other products using such a paint The present invention relates to a method for joining metal materials.

  Conventionally, a joined product obtained by joining and integrating metal materials (members) as various components or products in various fields ranging from household equipment to transportation equipment to industrial machinery. Two metal materials that give such a joint are mechanical bonding by rivets and the like, as well as material bonding represented by welding (melt bonding method, liquid-solid reaction bonding method, For example, a solid phase bonding method) or chemical bonding represented by adhesion (see Non-Patent Document 1).

  However, in the material bonding method represented by welding, which is employed for bonding between such metal materials, generally, the apparatus and operation for performing the bonding are enlarged and complicated, There is a problem that the consumption of heat energy for bonding is large, causing the material change for that purpose, and the bonding cost is high, and the chemical bonding technique represented by bonding. In that case, various adhesives have been proposed so far because the joining operation is easy and simple. For example, in Non-Patent Document 1, the thermosetting resin system and the thermoplastic resin system have been proposed. Various synthetic polymer adhesives such as rubber-based and composite-based adhesives have been clarified, but these conventional adhesives generally have poor heat resistance, insufficient adhesive strength, and special adhesives. Need surface modification treatment Were those inherent problems such as that.

  For example, in Patent Document 1, in order to obtain a metal member for bonding in which a metal surface is activated and a primer layer having excellent adhesion is firmly attached, energy is applied to the surface of the metal substrate by, for example, laser treatment. In addition, with the metal hydroxide formed on the surface of the substrate, a primer containing a predetermined compound is applied, and the compound in the formed primer layer is directly applied to the hydroxyl group of the metal hydroxide on the substrate surface. Although a technique for covalent bonding has been clarified, it is necessary to add a special surface modification treatment such as laser treatment to the surface of the base material, which makes the joining operation troublesome. In addition, there is an inherent problem that the cost for joining increases due to the need for an apparatus for reforming treatment.

JP 2010-5838 A

Edited by the Japan Institute of Metals, “Revised 6th edition Metal Handbook” (published by Maruzen Co., Ltd.), pages 991-1003

  Here, the present invention has been made in the background as described above, and the problem to be solved is that the two metal materials are subjected to any special surface modification treatment on their joint surfaces. A paint that can be easily and firmly joined without using the paint, and a coated metal material obtained by using the paint, and further, using such a paint, the two metal materials can be effectively and economically advantageous. The object is to provide a method of bonding.

  And, in order to solve the above-mentioned problems, the present invention can be suitably implemented in various aspects as listed below, and each aspect described below can be implemented in any combination. Can be adopted. It should be noted that the aspects or technical features of the present invention are not limited to those described below, and can be recognized based on the inventive concept that can be grasped from the entire description. Should be understood.

(1) In order to join the metal material to the metal material, a paint applied to at least one of the joint surfaces of the metal material is used.
A combination of up to 80% by weight of polybutylene terephthalate resin and 20% by weight or more of a hydroxyl group-containing polyester resin, together with these two types of resins, a curing agent having a ratio of 0 to 50% by weight with respect to the hydroxyl group-containing polyester resin A metal material-metal material bonding paint prepared by mixing in a solvent to dissolve such a hydroxyl group-containing polyester resin and further dissolving or finely dispersing a polybutylene terephthalate resin.
(2) The metal material-metal material joining paint according to the aspect (1), wherein the polybutylene terephthalate resin contains a fibrous or powdery inorganic filler.
(3) The metal material-metal material bonding paint according to the aspect (1) or (2), wherein the hydroxyl group-containing polyester resin has a number average molecular weight of 8000 or more and a glass transition point of 20 ° C. or more. .
(4) The metal material-metal material joint according to any one of the aspects (1) to (3), wherein the curing agent is selected from the group consisting of a blocked polyisocyanate compound, an amino resin, and a phenol resin. paint.
(5) The metal material according to any one of the aspects (1) to (4), wherein the solvent is a single solvent composed of isophorone or N-methyl-2-pyrrolidone or a mixed solvent containing the same as a main component. -Paint for joining metal materials.
(6) Any of the above aspects (1) to (5), wherein a curing catalyst is further added at a ratio of 0 to 1.0% by weight with respect to the total amount of the hydroxyl group-containing polyester resin and the curing agent. The metal material-metal material bonding paint according to claim 1.
(7) The embodiments (1) to (6), wherein the polybutylene terephthalate resin is precipitated by cooling a solution obtained by dissolving in the solvent by heating and dispersed as a fine solid. ) The metal material-metal material joining paint according to any one of the above.
(8) The paint according to any one of the above aspects (1) to (7) is applied to the joint surface of the metal material at a rate of 0.5 to 10 g / m ^2. Metal material-Painted metal material for joining metal materials.
(9) The painted metal material for joining a metal material to a metal material according to the aspect (8), wherein the paint layer formed by applying the paint is heat-treated and baked.
(10) The coated metal material for joining a metal material to a metal material according to the aspect (8) or (9), wherein the metal material is an aluminum material made of aluminum or an alloy thereof.
(11) The paint according to any one of the above aspects (1) to (7) is applied to each joining surface of two metal materials to be joined at a rate of 0.5 to 10 g / m ^2. Then, after forming the coating film by heating and drying, the two metal materials are joined to each other by overlapping, heating and pressurizing the coating surface of the two metal materials facing each other. A method for joining a metal material to a metal material, characterized in that:
(12) The paint according to any one of the above aspects (1) to (7) is applied to the joining surface of one of the two metal materials to be joined at a rate of 0.5 to 10 g / m ² . After coating and drying by heating, a coating film is formed, and the bonding surface of the other metal material is superimposed on the coating film forming surface of the obtained one metal material, and heated and heated. A method of joining a metal material and a metal material, characterized by joining the two metal materials by pressing.
(13) The coating material according to any one of the aspects (1) to (7) is applied to at least one of the joining surfaces of the two metal materials to be joined at a rate of 0.5 to 10 g / m ² . A method for joining a metal material and a metal material, characterized in that the two metal materials are joined together by applying them in a ratio while superimposing and heating the joining surfaces of the two metal materials facing each other.

  As described above, the metal material-metal material bonding paint according to the present invention uses a predetermined amount of two resin components, polybutylene terephthalate resin and hydroxyl group-containing polyester resin, for bonding the two metal materials. In addition, such a hydroxyl group-containing polyester resin is dissolved, and the polybutylene terephthalate resin is dissolved or dispersed in the form of fine solids or particles. In the presence of the two resin components, the other metal material can be easily and effectively joined to the predetermined joint surface of one metal material, and can be advantageously obtained as a strong integrated joint. It was possible to do.

  Moreover, when applying the coating material according to the present invention to the joint surface of the metal material, it is not necessary to apply any special surface modification treatment to the joint surface of the metal material, and it is applied as it is. And by joining the metal material to be joined under heating through the coating film to be formed, the reliable joining of the two metal materials can be effectively realized. It becomes. For this reason, the joining operation of the metal material according to the present invention can be carried out much more easily and economically advantageously than before.

  In addition, the coating material for joining metal materials according to the present invention has heat resistance by including polybutylene terephthalate resin as one of the resin components. For this reason, two metal materials using such a coating material are used. Since the joint obtained by bonding the joints can be effectively suppressed or prevented from lowering the joint strength even when exposed to high temperatures, the joint is used in a high temperature environment. As a product or component, for example, a feature that it can be advantageously employed as a heat exchanger or the like in which a heat transfer tube and a corrugated fin, a plate fin or the like are assembled can be exhibited.

  By the way, in such a metal-metal bonding paint according to the present invention, polybutylene terephthalate (PBT) resin, which is one of the essential components, enhances the adhesion to the metal and also provides heat resistance to the paint. As is well known, it is a thermoplastic, crystalline resin obtained by polycondensation of terephthalic acid or dimethyl terephthalate and 1,4-butanediol as main components. In the present invention, various known ones are used as they are. Moreover, in order to give further heat resistance etc. to this PBT resin, fibrous or powdery inorganic fillers, such as glass fiber, a glass bead, and powder glass, will be contained suitably. In addition, as a content of this inorganic filler, an appropriate ratio is selected as long as it does not adversely affect the paint, but it is generally included in a ratio of up to 50% by weight.

  Various PBT resins containing or not containing this inorganic filler are commercially available, for example, Toraycon 1401X06 (without filler), Toraycon 1401X04 (without filler) manufactured by Toray Industries, Inc. , Toraycon 1201G-15 (containing 15% glass fiber), Toraycon 1101G-30 (containing 30% glass fiber); NOVADURAN 5008 (without filler), NOVADURAN 5020 (without filler), manufactured by Mitsubishi Engineering Plastics Co., Ltd. NOVADURAN 5026 (containing no filler), NOVADURAN 5010G15 (containing 15% glass fiber), NOVADURAN 5010G45 (containing 45% glass fiber); DURANEX 2002 (without filler), DURANEX 2000 (manufactured by Polyplastics) Phi Over-free), DURANEX 3105 (15% glass fiber content), can be exemplified such DURANEX 3405 (45% glass fiber content), and thus is suitably selected from among them.

  Further, the hydroxyl group-containing polyester resin, which is another essential component of the paint according to the present invention, is a known polymer containing a hydroxyl group, which is a polycondensate obtained mainly from a polybasic acid component and a polyhydric alcohol component. In addition, in cooperation with the PBT resin that is dissolved or finely dispersed in the paint, it exhibits an excellent adhesive force to the metal material to be joined, and the PBT resin is dispersed in the form of particles. In forming the body, the particles can be formed more easily and the effect of stabilizing can be exhibited. In addition, as this hydroxyl-containing polyester resin, that whose number average molecular weight (Mn) is 8000 or more will be used suitably. This is because the tensile shear bond strength tends to decrease as the number average molecular weight decreases. Moreover, as a glass transition temperature (Tg) of this hydroxyl-containing polyester resin, it is desirable that it is 20 degreeC or more, Furthermore, what is 45 degreeC or more will be used more advantageously. Here, when the glass transition temperature is lower than 20 ° C., the pre-coated metal material formed by applying the paint according to the present invention, particularly when the plate-like material is stacked and stored, the anti-blocking property of these coated metal materials. This may reduce the workability and cause problems in workability and handling.

  In addition, various hydroxyl group-containing polyester resins used in the present invention as described above are commercially available, and are appropriately selected and used. For example, Byron 200 (Tg: 67 ° C., hydroxyl value: 6 KOH mg / g, Mn: 17000), Byron 290 (Tg: 72 ° C., hydroxyl value: 5 KOH mg / g, Mn: 22000), which are products of Toyobo Co., Ltd., Byron 660 (Tg: 55 ° C., hydroxyl value: 14 KOH mg / g, Mn: 8000), Byron GK880 (Tg: 84 ° C., hydroxyl value: 5 KOH mg / g, Mn: 18000), Byron BX-7000 (Tg: 60 ° C., Hydroxyl value: 2 KOH mg / g, Mn: 32000), Byron GK330 (Tg: 16 ° C., hydroxyl value: 9 KOH mg / g, Mn: 17000); Elitel UE-9200 (Tg: 65 ° C., hydroxyl value) manufactured by Unitika Ltd. : 6KOHmg / g, Mn: 15000), Elitel UE-9600 (Tg: 70 ° C, Hydroxic acid Value: 8KOHmg / g, Mn: 18000) and the like can be mentioned.

  The PBT resin and the hydroxyl group-containing polyester resin are used in combination in the paint according to the present invention so that the former is in a proportion of up to 80% by weight, and therefore the latter is in a proportion of 20% by weight or more. It will be. When the PBT resin exceeds 80% by weight in the blending ratio of these two resin components, it becomes difficult to dissolve with a solvent or the blending amount of the hydroxyl group-containing polyester resin is reduced. Insufficient dispersion causes problems that make it difficult to achieve the object of the present invention. It should be noted that the PBT resin is preferably used in a proportion of at least 5% by weight in the coating material in order to more fully exhibit the tensile shear adhesive strength between the two metal materials joined by the coating material according to the present invention. . The PBT resin and the hydroxyl group-containing polyester resin are preferably used in proportions of 5 to 70% by weight and 95 to 30% by weight, respectively.

  In the coating material according to the present invention, a known curing agent capable of curing the hydroxyl group-containing polyester resin is preferably 5 to 30% by weight in a proportion of 0 to 50% by weight with respect to the hydroxyl group-containing polyester resin. In this ratio, it is added and blended. By adding such a curing agent, the tensile shear bond strength between two bonded metal materials can be further effectively improved. However, when the amount of such a curing agent increases, Excessive addition should be avoided because it tends to decrease. And in this invention, as such a hardening | curing agent, well-known various things, such as a blocked polyisocyanate compound, an amino resin, a phenol resin, will be used suitably, Among these, adhesive force As a curing agent that easily develops, a blocked polyisocyanate compound or an amino resin is preferably used.

  Here, the blocked polyisocyanate compound used as such a curing agent is obtained by blocking the isocyanate group of the polyisocyanate compound with a blocking agent. And as the polyisocyanate compound, for example, aromatic diisocyanate compounds such as tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate; aliphatic diisocyanate compounds such as hexamethylene diisocyanate, trimethylhexane diisocyanate; isophorone diisocyanate, hydrogenated Cycloaliphatic diisocyanate compounds such as xylylene diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), methylcyclohexane-2,4 (or 2,6) -diisocyanate, 1,3- (isocyanatomethyl) cyclohexane; An adduct of a compound and a polyhydric alcohol, a low molecular weight polyester resin or water, or the polyisocyanate Cyclic polymers between bets compounds, further, may be mentioned isocyanate biuret like. Among these polyisocyanate compounds, aliphatic diisocyanate compounds are preferably used in terms of hygiene.

  Further, the blocking agent for blocking the polyisocyanate compound can be appropriately selected from various known blocking agents, but the drying temperature of the paint according to the present invention can be used. In view of the solvent, since it is desirable that the temperature is 200 ° C. or higher, the blocking agent is selected so that the dissociation temperature of the blocked material is 100 to 200 ° C. in order to improve the stability during paint storage. It is desirable. Examples of such blocking agents include oxime blocking agents such as formamide oxime, acetoxime, methyl ethyl ketoxime, cyclohexanone oxime, and acetoaldoxime; lactams such as ε-caprolactam, β-valerolactam, and γ-butyrolactam. Blocking agents; alcohol blocking agents such as methanol, ethanol, isopropyl alcohol, n-butyl alcohol, ethylene glycol monobutyl ether; active methylene blocking agents such as dimethyl malonate, ethyl acetoacetate, and acetylacetone I can do it.

  Blocked polyisocyanate compounds obtained by blocking isocyanate groups with this blocking agent are also commercially available from various companies. For example, Duranate 17B-60PX (solid content 60%), Duranate manufactured by Asahi Kasei Chemicals Corporation. TPA-B80E (solid content 80%), Duranate MF-B60X (solid content 60%), Duranate E402-B80T (solid content 80%); Vestagon B1530 (solid content 100%) manufactured by Degussa Japan, Vestagon B1065 ( Solid content 100%), Vesta nut B1358 (solid content 100%), Vesta nut B1370 (solid content 60%), and the like, which are appropriately selected.

  Moreover, as an amino resin which is one of the above-described curing agents, for example, urea resin, melamine resin, benzoguanamine resin and the like can be used, and more specifically, methylated urea resin, methyl etherified urea, and the like. Resins, butyl etherified urea resins, mixed etherified urea resins of methyl ether and butyl ether; melamine resins such as methylol melamine resins, methyl etherified melamine resins, butyl etherified melamine resins, mixed etherified melamine resins of methyl ether and butyl ether; Benzoguanamine resin, methyl ether benzoguanamine resin, butyl ether benzoguanamine resin, mixed ether benzoguanamine resin of methyl ether and butyl ether, and the like. Commercially available products include, for example, Cymel 303 (solid content 100%), Cymel 235 (solid content 100%), Mycoat 506 (solid content 100%), Cymel 1123 (solid content 100%) manufactured by Nippon Cytec Industries, Ltd. ), UFR65 (solid content: 100%), UFR300 (solid content: 60%), or the like can be used.

  Furthermore, for the phenolic resin as the curing agent, a resol type phenolic resin, preferably a metacresol resin, is preferably used. For example, Sumitrite Resin PR-53893A (solid content 50 manufactured by Sumitomo Durez Co., Ltd.) %) Etc. can be used.

  In addition, the coating according to the present invention is added with the curing agent, if necessary, together with the above curing agent, thereby effectively improving the tensile shear bond strength between the two metal materials to be joined. Can be achieved. In this case, an appropriate curing catalyst is appropriately selected depending on the type of curing agent used. For example, when the curing material is a blocked polyisocyanate compound, known organometallic catalysts such as tin, zirconium, aluminum and bismuth are preferably used, and amino resins and phenol resins are used as curing agents. When used, known acids such as phosphoric acid and sulfonic acid are preferably used. In addition, as the addition amount, it is desirable to use in such a ratio that it is 1% by weight or less of the total amount of the hydroxyl group-containing polyester resin and the curing agent.

  And the coating material according to this invention will be prepared in a liquid form using a suitable solvent in order to apply | coat the above-mentioned PBT resin, a hydroxyl-containing polyester resin, a hardening | curing agent etc. uniformly to the metal material surface. However, since the PBT resin is used in a dissolved form and is difficult to dissolve in a solvent, it is preferably present in a form finely dispersed in the solvent, and thus, according to the present invention. An effective joint between two metal materials can be easily realized. Such fine dispersion of the PBT resin can be carried out by a known appropriate method. In particular, in the present invention, the PBT resin is added to a predetermined solvent and then heated. The PBT resin is dissolved in a solvent, and the obtained solution is cooled to be precipitated, so that it can be dispersed as fine solid particles, generally in a size of about 200 μm or less. It is desirable.

  In addition, as a solvent used for preparation of this coating material, it can select suitably from well-known solvents, such as o-chlorophenol, dichlorobenzene, benzyl alcohol, a phenol / tetrachloroethane mixed solvent, However, especially with a single solvent, , Isophorone or N-methyl-2-pyrrolidone is preferably used, and the mixed solvent is mainly composed of isophorone or N-methyl-2-pyrrolidone, particularly in a proportion of 60% or more, and has a boiling point of 200 ° C. The composition having the above is preferably used. In this connection, the solvent mixed with isophorone or N-methyl-2-pyrrolidone generally has a boiling point of 200 ° C. or higher, and particularly has a solubility parameter (δ) of 9-10. For example, diethylene glycol monoethyl ether (boiling point 202 ° C., δ = 9.6), diethylene glycol (boiling point 245 ° C., δ = 9.1), DBE (DuPont products; dimethyl glutarate, dimethyl adipate and succinic acid) A mixture with dimethyl, a boiling point of 205 ° C., δ = 9.4) and the like are preferably used.

  The metal material (member) to which the paint according to the present invention prepared in this way is applied has a predetermined shape, and has various shapes such as a plate material, a shape material, and a bar material. Be targeted. Furthermore, the material is preferably made of aluminum or an alloy thereof, but the same effect can be obtained even if it is made of other metal materials such as iron or steel material, copper or alloy material thereof. I can do it. In addition, the paint according to the present invention can be effectively applied to the joining of metal materials of different metal materials.

Further, when applying the paint according to the present invention to the joint surfaces to be joined with the metal material, known coating techniques such as dipping, spraying, roll coating, etc. are appropriately employed and formed by the coating. The paint layer is dried and baked by being heated using a known heating means such as hot air drying, infrared irradiation, high frequency heating or the like. In this way, the coating film formed on the predetermined joint surface of the metal material has an appropriate thickness, but in the present invention, the solid coating is applied by applying the paint according to the present invention. The target coating film is formed at such a thickness that the proportion is 0.5 to 10 g / m ² . This is because when the coating amount decreases (thickness decreases), the bonding strength decreases, and the object of the present invention cannot be sufficiently achieved, and the coating amount becomes 10 g / m ² . Even if it exceeds, only the coating cost increases, and the bonding strength is not improved.

Then, the coating material according to the present invention is applied as described above, and the desired coating layer or coating film is formed on one metal material through the coating layer or coating film. The other metal material is bonded. As one specific example of such a bonding method, the paint according to the present invention as described above is applied to each bonding surface of two metal materials to be bonded. After coating a predetermined coating film by applying at a rate of 0.5 to 10 g / m ² , heating and drying, and further baking, respectively, the coating film forming surfaces of these two coated metal materials A method is adopted in which the two painted metal materials are joined by overlapping, heating, and pressurizing each other.

  According to such a joining method, a coating film of sufficient thickness is interposed between the metal materials since the coating films of the two coated metal materials are overlapped and heat-pressed. As a result, stronger joining of these metal materials can be realized, and joining is performed using a coated metal material having a coating film solidified by drying (baking). In addition to making the painted metal material easier to handle, the plate-like metal materials can be used together without any consideration of the problem of insufficient joining due to the residual solvent in the central portion of the overlapped portion. This can also be performed effectively.

  In addition, unlike such a joining method, a method of using one of the above-described painted metal materials and superimposing it on a non-painted metal material and joining them in the same manner can be advantageously employed.

That is, the paint according to the present invention described above is applied to the joint surface of one of the two metal materials to be joined at a rate of 0.5 to 10 g / m ² and dried by heating to form a coating film. After forming, the joint surface of the other metal material (non-paint metal material) is placed on the coating film forming surface of one metal material (paint metal material) obtained, and heated and pressurized. Thus, it is a technique of joining these two metal materials, and by this, the same operation and effect as the above-described bonding method can be enjoyed except for the operation and effect by the superposition of the coating films.

Furthermore, in the present invention, in addition to the two joining methods described above, the two metal materials are joined immediately without drying the paint layer formed by applying the paint according to the present invention. It is also possible to make it. Specifically, the coating material according to the present invention is supplied and applied at a rate of 0.5 to 10 g / m ^{2 on} at least one of the joining surfaces of the two metal materials to be joined. It is a technique that consists of joining two metal materials together by heating the two metal materials facing each other, heating them, and without applying operations such as heating and drying. Later, it is possible to immediately enjoy the advantage of being able to join metal materials.

  In any of the joining methods described above, heating and further pressurization (crimping) are required for joining two metal materials superimposed via a paint film or paint layer made of the paint according to the present invention. As a result, the PBT resin in the coating film or paint layer is plasticized and melted, and the crosslinking and curing of the hydroxyl group-containing polyester resin is promoted. The metal material can be joined more firmly, and can be advantageously obtained as an excellent integrated joint.

  Hereinafter, representative examples of the present invention will be shown to clarify the present invention more specifically, but the present invention is not limited by the description of such examples. It goes without saying. In addition to the following examples, the present invention includes various changes and modifications based on the knowledge of those skilled in the art without departing from the spirit of the present invention, in addition to the specific description described above. It should be understood that improvements can be made.

(1) Preparation of PBT resin dispersion A 1-L flask, together with a commercially available PBT resin (Toraycon 1401X06 manufactured by Toray Industries, Inc.), one each of the hydroxyl group-containing polyester resin shown in Table 1 below and the solvent shown in Table 2 below These were charged in the proportions shown in Tables 3 to 5 below, and the liquid temperature was raised while heating and stirring to dissolve the PBT resin together with the hydroxyl group-containing polyester resin. The dissolution temperature was all 200 ° C. Next, by cooling the obtained resin solution, in addition to various dispersions in which the PBT resin is finely dispersed in the hydroxyl group-containing polyester resin solution, one of these resins is completely dissolved in the solvent. A uniform resin solution was obtained. In Experimental Examples 21, 22, and 53, 54, a commercially available adhesive (Mitsui Chemicals Unistar R-300) containing modified polypropylene as the main component was used as the paint 1, and Experimental Examples 43, 44. In 55 and 56, each coating film was formed using a commercially available adhesive (Byron GK-88CS manufactured by Toyobo Co., Ltd.) mainly composed of a thermoplastic polyester resin as the coating material 2.

The viscosity of the obtained various PBT dispersions and the like is measured with a B-type viscometer (the rotor uses No. 3) at 25 ° C., while the PBT resin in each of the dispersions and the like is measured. The dispersion state was observed and evaluated based on the following criteria, and the results are shown in Tables 3 to 5 below.
Complete dissolution: The liquid is transparent and no dispersion is present. ○: Dispersion in which the average particle size is less than 10 μm. ○ Δ: Dispersion of dispersed particles having an average particle size of 10 to 30 μm. Δ: Average Dispersion of dispersed particles having a particle size exceeding 30 μm ×: Resin is agglomerated and not dispersed

(2) Preparation of paint Using various dispersions obtained in the above (1) and stirring them, the blocked polyisocyanate compound (Degussa Japan Co., Ltd. Vesta nut B1379) was used as a curing agent. These were added as necessary under the conditions shown in Tables 3 to 5 below to prepare various paints according to Experimental Examples 1 to 56. In addition, about Experimental Examples 15-18, although it became the dispersion liquid which PBT resin disperse | distributed to the lump form, it was used as it was as a coating material.

(3) Paint evaluation-I
Using the various paints shown in Table 3 prepared in the above (2), each was applied to an aluminum alloy plate (A5182-H24) having a thickness of 1.0 mm using a bar coater, as shown in Table 6 below. Various aluminum alloy coating plates are coated by applying the various coating amounts shown (solid content; coating amount) and baking in an oven at 260 ° C. (maximum temperature) for 30 seconds (baking time). (Pre-coated plate) was prepared.

  Next, the aluminum alloy coated plate produced by the above method was cut into a size of 20 mm × 70 mm. Then, the two cut aluminum alloy coated plates were heated on a hot plate heated to 200 ° C. for 1 minute 50 seconds, and then immediately, one painted plate was placed on the other painted plate. After overlapping with 10 mm × 20 mm end overlapping portions so that their coated surfaces face each other, and then placing a 1 kgf weight heated to 200 ° C. in advance and holding for 15 seconds, Various adhesion test pieces were produced by taking out from the hot plate and allowing to cool.

  And about this obtained adhesion test piece, at the atmospheric temperature: 25 degreeC or 180 degreeC, the edge part of the two laminated | stacked aluminum alloy coating plates was each tensioned | pulled (tensile speed). : 5 mm / min), the tensile shear bond strength was measured, and the results are also shown in Table 6 below.

  As apparent from the results in Table 6, in each paint according to Experimental Examples 1 to 12 according to the present invention, the tensile shear adhesive strength between the aluminum alloy coated plates after the respective coatings is the same as that during the tensile test. Needless to say, the atmospheric temperature is 25 ° C., and even at 180 ° C., the pressure is 7 MPa or more, which indicates that they are bonded with high adhesiveness. In particular, high adhesive strength can be secured even at high temperatures.

  On the other hand, in the cases of Experimental Examples 13 and 14, since the amount of the coating film applied to the aluminum alloy plate is small, sufficient tensile shear adhesive strength cannot be exhibited. In the case of Examples 15 to 18, since the dispersion of the PBT resin was insufficient and it was difficult to form an effective coating film, there was no adhesive force, and the tensile shear adhesive strength was 0. It was. In addition, as shown in Experimental Examples 19 and 20, when the atmospheric temperature during the tensile test is 180 ° C., it is also clear that the tensile shear bond strength is completely lost when the coating amount is small. It was. Furthermore, even when a commercially available adhesive was used, as shown in Experimental Example 22, no tensile shear adhesive strength could be recognized.

(4) Paint evaluation-II
Using the various paints shown in Table 4 prepared in the above (2), each was applied to an aluminum alloy plate (A5182-H24) having a thickness of 1.0 mm using a bar coater and in Table 7 below. After coating so that the various coating amounts (solid content; coating amount) shown, it was baked in an oven at 260 ° C. (maximum temperature reached) for 30 seconds to prepare various aluminum alloy coated plates. .

  Next, the aluminum alloy coated plate produced by such a method was cut into a size of 20 mm × 70 mm. And, this cut aluminum alloy coated plate is not coated, on a hot plate heated to 200 ° C., with an aluminum alloy plate similar to the above having a thickness of 1.0 mm and a size of 20 mm × 70 mm, Immediately after heating for 1 minute 50 seconds, place the uncoated plate on the coated plate so that the end overlaps 10 mm × 20 mm, and then place a 1 kgf weight heated to 200 ° C. from above, After holding for 15 seconds, it was taken out from the hot plate and allowed to cool to prepare various adhesion test pieces.

  Thereafter, each of the obtained various adhesive test pieces was subjected to a tensile test in an atmosphere of 25 ° C. or 180 ° C. in the same manner as in the above (3) (tensile speed: 5 mm / min), and ruptured. The load was measured, and the results are shown in Table 7 below.

  As is apparent from the results in Table 7, in each paint according to Experimental Examples 23 to 34 according to the present invention, the tensile shear bond strength between the painted aluminum alloy sheet after coating and the uncoated aluminum alloy sheet is as follows. However, when the atmospheric temperature during the tensile test is 25 ° C., it is 7 MPa or higher even at 180 ° C., indicating that they are bonded with high adhesiveness. It was also revealed that excellent adhesiveness was exhibited also in the adhesiveness.

  On the other hand, as shown in Experimental Examples 35, 36 and 41, 42, when the coating amount is small and a coating film having a sufficient thickness cannot be formed, sufficient tensile shear adhesive strength is obtained. In addition, when the ambient temperature during the tensile test reached 180 ° C., the adhesive strength was lost and the tensile shear adhesive strength was zero. Further, in the case of Experimental Examples 37 to 40, the dispersion of the PBT resin was insufficient and an effective coating film could not be formed, so that the adhesive force was hardly exhibited. Furthermore, as shown in Experimental Examples 43 and 44, when an adhesive using only a thermoplastic polyester resin is used, it exhibits a certain degree of adhesive strength at room temperature (25 ° C.), but the temperature is high. (180 ° C.), the adhesive force could not be exhibited at all.

(5) Evaluation of paint-III
Using the various paints shown in Table 5 prepared in (2) above, a thickness: 1.0 mm of 20 mm × 70 mm aluminum alloy plate (A5182-H24), and a diameter: 15 mm × Joining to a 70 mm long aluminum alloy rod (A6063-F) was performed. That is, an aluminum alloy rod is stacked on such an aluminum alloy plate in a length of 10 mm, and each paint is supplied to the contact portion with a dropper, and then stored in an oven heated to 250 ° C. while maintaining the state. After being held for 5 minutes, it was allowed to cool to produce various adhesion test pieces.

  Subsequently, the obtained adhesion test piece was subjected to a tensile test in an atmosphere of 25 ° C. or 180 ° C. (tensile speed: 5 mm / min), and the breaking load was measured. The results are also shown in Table 8 below. It was.

  As is clear from the results of Table 8, in each paint according to Experimental Examples 45 to 50 according to the present invention, the tensile shear bond strength between the aluminum alloy plate and the aluminum alloy rod is 25 ° C. at an ambient temperature. In addition, it was revealed that even at a high atmospheric temperature of 180 ° C., it exhibits high adhesion.

On the other hand, when the paints according to Experimental Examples 51 to 56 were used, no adhesive strength was observed, and although a certain degree of adhesive strength was exhibited in an atmosphere at 25 ° C., 180 It was revealed that the adhesive strength was completely lost under the atmosphere of ° C.

Claims (14)

In order to join a metal material and a metal material, a paint applied to at least one of the joint surfaces of the metal material,
A combination of up to 80% by weight of polybutylene terephthalate resin and 20% by weight or more of a hydroxyl group-containing polyester resin (excluding polybutylene terephthalate resin) is combined with these two resins and 0 to 50% by weight with respect to the hydroxyl group-containing polyester resin. % Of a metal, which is prepared by dissolving a hydroxyl group-containing polyester resin in a solvent, and further dissolving or finely dispersing a polybutylene terephthalate resin. Material-metal material paint.   The metal material-metal material bonding paint according to claim 1, wherein the polybutylene terephthalate resin contains a fibrous or powdery inorganic filler.   The metal material-metal material coating material according to claim 1, wherein the hydroxyl group-containing polyester resin has a number average molecular weight of 8000 or more and a glass transition point of 20 ° C. or more. The metal material-metal material bonding paint according to any one of claims 1 to 3, wherein the hydroxyl group-containing polyester resin has a hydroxyl value of 2 to 14 KOHmg / g. The metal material-metal material bonding paint according to any one of claims 1 to 4 , wherein the curing agent is selected from the group consisting of a blocked polyisocyanate compound, an amino resin, and a phenol resin. 6. The metal material-metal material joint according to any one of claims 1 to 5 , wherein the solvent is a single solvent composed of isophorone or N-methyl-2-pyrrolidone or a mixed solvent containing the same as a main component. paint. The total amount of the curing agent and the hydroxyl group-containing polyester resin, curing catalyst, further, according to any one of claims 1 to 6 is added in an amount of 0 to 1.0 wt% Metal material-metal material bonding paint. The polybutylene terephthalate resin, the solution obtained is dissolved in the solvent by heating are caused to precipitate by cooling the any of claims 1 to 7 are dispersed as a fine solid 1 Metal material-metal material joining paint as described in item 4. The bonding surface of the metal material, a metal material coating according to any one of claims 1 to 8, characterized in that it is applied at a rate of 0.5 to 10 g / m ² - metallic materials Painted metal material for bonding. The metal material-metal material-coated metal material for bonding according to claim 9 , wherein the paint layer formed by applying the paint is heat-treated and baked. The metal material-metal material-coated metal material for joining according to claim 9 or 10 , wherein the metal material is an aluminum material made of aluminum or an alloy thereof. The paint according to any one of claims 1 to 8 is applied to each joining surface of two metal materials to be joined at a rate of 0.5 to 10 g / m ² , and dried by heating. After forming the coating film respectively, the two metal materials are bonded to each other by overlapping, heating and pressurizing the coating formation surfaces of the two metal materials facing each other. To join metal material to metal material. The paint according to any one of claims 1 to 8 is applied to the joining surface of one of the two metal materials to be joined at a rate of 0.5 to 10 g / m ² and heated. After forming the coating film by drying, the bonding surface of the other metal material is overlapped on the coating film forming surface of the obtained one metal material, and heated / pressurized to superimpose them. A method for joining metal materials to each other, characterized by joining two metal materials. One of applying the paint according to any one of claims 1 to 8 at a rate of 0.5 to 10 g / m ^{2 on} at least one of the two metal materials to be joined. A joining method of a metal material and a metal material, wherein the joining surfaces of the two metal materials are opposed to each other, overlapped and heated to join the two metal materials.