JP6344021B2 - Adhesive composition for metal member and thermoplastic resin-coated metal member using the same - Google Patents

Description

  The present invention relates to an adhesive composition for metal members and a thermoplastic resin-coated metal member using the same.

  Thermoplastic resin-coated metal members are often used in fields such as home appliances and building materials because of their high workability and design. Thermoplastic resin-coated metal members are used not only for interior wall materials such as unit bath wall materials and door materials, but also for external wall materials and members that require corrosion resistance. In recent years, thermoplastic resin-coated metal members have also been used for building materials in harsh environments such as the seabed, extremely cold regions, and the tropics.

  Generally, a thermoplastic resin-coated metal member is formed by curing a paint containing a thermoplastic resin composition applied to the surface of a metal member to form a cured film, or by laminating a thermoplastic resin film on a metal member. Have been made. In addition, an adhesive is used to adhere the metal member and the thermoplastic resin film (or cured film).

  The adhesive composition used for the thermoplastic resin-coated metal member is required to have improved adhesiveness, rust prevention property, especially hot water resistance, compared to the conventional use of the thermoplastic resin-coated metal member as described above. Yes.

  In order to satisfy such a requirement, for example, when a metal member is coated with a thermoplastic resin layer, an adhesive composition comprising an acrylic adhesive and / or a phenol adhesive is used on the surface of the metal member. It has been proposed to form an adhesive layer (Patent Document 1). According to the adhesive composition described in Patent Document 1, an adhesive layer having excellent water resistance is formed as compared with a conventional resin-coated metal member in which an adhesive polyolefin resin is directly fused to the surface of a metal member. Is done. For this reason, an adhesive composition with improved adhesion and water resistance between the skin layer and the metal member can be realized.

JP 2006-68908 A

  However, the adhesive composition described in Patent Document 1 has not been studied for adhesiveness and hot water resistance when exposed to hot water close to the boiling state, and has room for improvement.

  The present invention has been made in view of the circumstances as described above, and an adhesive composition for a metal member capable of exhibiting excellent hot water resistance while maintaining adhesion and rust prevention, and this adhesion It is an object of the present invention to provide a thermoplastic resin-coated metal member in which a thermoplastic resin coating and a metal member are bonded by an agent composition.

  In order to solve the above problems, an adhesive composition for a metal member of the present invention is an adhesive composition for a metal member that bonds a thermoplastic resin coating and a metal member, and is a modified urea-based or unsaturated polyamino It is characterized by containing an anti-settling agent which is at least one of amide type, a plate-like filler, a thermoplastic resin, and a thermosetting resin.

  In the adhesive composition for a metal member of the present invention, it is preferable that the thermoplastic resin is an acrylic resin and the thermosetting resin is a phenol resin.

  In the metal member adhesive composition of the present invention, the dispersed particle diameter of the plate-like filler in the metal member adhesive composition is 50 μm or less, and the aspect ratio is in the range of 2 to 100. preferable.

  In the adhesive composition for a metal member of the present invention, the plate-like filler may be at least one selected from the group consisting of plate-like magnesium phosphate, plate-like aluminum phosphate, and plate-like zinc phosphate. preferable.

  In addition, the thermoplastic resin-coated metal member of the present invention is characterized in that the thermoplastic resin coating and the metal member are bonded via the above-described adhesive composition for a metal member.

  According to the adhesive composition for a metal member of the present invention and a thermoplastic resin-coated metal member using the same, excellent hot water resistance can be exhibited while maintaining adhesion and rust prevention.

  Below, the adhesive composition for metal members of this invention and a thermoplastic resin coating | coated metal member using the same are demonstrated in detail.

  The adhesive composition for a metal member is an adhesive containing an anti-settling agent that is at least one of a modified urea type or an unsaturated polyaminoamide type, a plate-like filler, a thermoplastic resin, and a thermosetting resin. Agent composition. Further, the thermoplastic resin-coated metal member is one in which the thermoplastic resin coating and the metal member are bonded via the above-mentioned adhesive composition.

  The modified urea-based and unsaturated polyaminoamide-based anti-settling agents both disperse the plate-like filler described later in the metal member adhesive composition even under long-term storage. Improve the stability. In addition, modified urea-based and unsaturated polyaminoamide-based anti-settling agents can quickly and uniformly plate-like fillers in metal member adhesive compositions without stirring the metal member adhesive composition on site for a long time. To improve the work efficiency. The use of an anti-settling agent which is at least one of such a modified urea type or unsaturated polyaminoamide type is particularly noted in the adhesive composition for metal members.

  Examples of the modified urea-based or unsaturated polyaminoamide-based precipitation inhibitor include, for example, modified urea, urea-modified urethane, urea-modified medium polar polyamide, urea-modified low-polar polyamide, unsaturated polyaminoamide and low-molecular weight polyester acid salt, polyamino Examples include amide polycarboxylates and the like. Preferably, modified urea, unsaturated polyaminoamide, a salt of low molecular weight polyester acid, and the like are exemplified. These can be used alone or in combination of two or more.

  Examples of commercially available modified urea include BYK-410 (Bic Chemie Japan Co., Ltd.).

  Examples of commercially available salts of unsaturated polyaminoamide and low molecular weight polyester acid include ANTI-TERRA-U (ATU), ANTI-TERRA-U 100 (ATU100) (BIC Chemie Japan Co., Ltd.) and the like.

  The modified urea-based anti-settling agent precipitates in the adhesive composition for a metal member and forms a three-dimensional structure held by hydrogen bonds while forming needle crystals. For this reason, thixotropic fluidity arises and sedimentation of the plate-like filler in the adhesive composition for metal members is prevented. Moreover, the sagging prevention property of the adhesive composition for metal members is also improved.

  On the other hand, the unsaturated polyaminoamide antisettling agent is adsorbed on the surface of the plate-like filler in the adhesive composition for metal members, and the plate-like filler is dispersed and stabilized by steric hindrance between the amides.

  The content ratio of the modified urea-based or unsaturated polyaminoamide-based anti-settling agent in the metal member adhesive composition is, for example, in the range of 0.1% by mass to 3% by mass of the entire metal member resin composition. Is done. Preferably the range of 0.1 mass%-2 mass%, More preferably, the range of 0.3 mass%-1 mass% is illustrated. When the content ratio of the modified urea-based or unsaturated polyaminoamide-based anti-settling agent is within the above range, desired stability and on-site work efficiency are good. If the content of the modified urea-based or unsaturated polyaminoamide-based anti-settling agent is less than 0.1% by mass, the anti-settling effect is not sufficiently exhibited, and the on-site redispersibility is likely to deteriorate. Become. On the other hand, when the content ratio of the modified urea-based or unsaturated polyaminoamide-based anti-settling agent exceeds 3% by mass, the viscosity of the adhesive composition for a metal member increases, so that the coating property tends to be lowered. In addition, when it contains both modified urea type and unsaturated polyaminoamide type antisettling agents, it is preferable to make the total amount of both into the said range.

  The plate-like filler relieves shrinkage stress due to heat of the adhesive composition for metal members and improves the strength of the cured adhesive composition for metal members. In addition, since the plate-like filler is uniformly dispersed in the adhesive composition for metal members, it prevents hot water from penetrating into the bonding surface between the adhesive composition for metal members and the metal member and exhibits hot water resistance. be able to. The use of such a plate-like filler is particularly noted in the adhesive composition for metal members.

  Examples of the plate-like filler include talc, kaolin, mica, clay, sericite, glass flake, synthetic hydrotalcite, various metal foils, graphite, molybdenum disulfide, tungsten disulfide, and boron nitride. Moreover, plate-like iron oxide, plate-like calcium carbonate, plate-like aluminum hydroxide, plate-like zinc phosphate, plate-like aluminum phosphate, plate-like magnesium phosphate, plate-like calcium phosphate and the like are exemplified. Preferably, talc, mica, plate-like zinc phosphate, plate-like aluminum phosphate, plate-like magnesium phosphate, plate-like calcium phosphate and the like are exemplified. More preferably, plate-like zinc phosphate, plate-like aluminum phosphate, plate-like magnesium phosphate, etc. which are excellent in rust prevention in addition to hot water are exemplified.

  Examples of commercially available talc include MS-P, MSW, MS, SWE, MSG, SW, and SSS (Nippon Talc Co., Ltd.).

  Examples of the plate-like zinc phosphate include compounds such as zinc phosphate, zinc phosphate tetrahydrate, and zinc phosphite.

  Examples of commercially available plate-like zinc phosphate include ZP-DL, P-WF, P-W-2, D-1, ZP-50S, ZP-SB, ZP-HS, MZP-500, and MP-620PMG. ZP-600 (manufactured by Kikuchi Color Co., Ltd.), EXPERT NP-530 (manufactured by Toho Pigment Co., Ltd.) and the like.

  Examples of the plate-like aluminum phosphate include compounds such as aluminum tripolyphosphate and aluminum phosphite. As a commercial item of plate-like aluminum phosphate, for example, K-white # 82, # 84, # 84S, # 85, # 94, # 105 (manufactured by Teika Co., Ltd.), EXPERT NP-1102 (manufactured by Toho Pigment Co., Ltd.) And the like.

  Examples of the plate-like magnesium phosphate include compounds such as magnesium zinc phosphate, primary magnesium phosphate, secondary magnesium phosphate, tertiary magnesium phosphate, and magnesium phosphite. As a commercial item of plate-like magnesium phosphate, LF bousei PMG, LF bousei MZP-500 (made by Kikuchi Color Co., Ltd.) etc. are illustrated, for example.

  As a commercial item of plate-like calcium phosphate, EXPERT NP-1020 (made by Toho Pigment Co., Ltd.) etc. are illustrated, for example.

  The plate-like filler containing the above-mentioned phosphate as a main component gradually elutes phosphate ions, chelates iron, zinc, and the like to passivate the surface. Other ionic compounds such as silica, zinc, magnesium, and calcium can be modified on the surface of the plate-like filler containing phosphate as a main component. When a hot dip galvanized metal member is used as the metal member, a surface modified with magnesium, silica or the like is preferably used.

  In particular, magnesium phosphate elutes magnesium ions from particles, and the eluted magnesium ions form a protective film on the surface of the metal member, thereby suppressing metal corrosion.

  As the plate-like filler, those having a dispersed particle size of 50 μm or less and an aspect ratio in the range of 2 to 100 are preferably exemplified. Here, the dispersed particle diameter is an average particle diameter of particles (secondary particles) dispersed in the adhesive composition in a state where plate-like filler particles (primary particles) are aggregated. If the dispersed particle diameter is within the above range, the shrinkage stress of the resin can be relaxed, contributing to improvement of hot water resistance and good adhesion. Moreover, since the intensity | strength of plate-shaped filler itself will be maintained if an aspect ratio is in the said range, the intensity | strength of the hardened | cured adhesive composition for metal members can be maintained. On the other hand, when the aspect ratio is less than 2, the filler has a spherical shape or a shape close to a spherical shape. Therefore, it becomes difficult to effectively function to alleviate the shrinkage stress of the resin, and it is difficult to improve the hot water resistance. On the other hand, when the aspect ratio exceeds 100, the strength of the filler itself tends to decrease, and the strength of the adhesive tends to decrease.

  The content ratio of the plate-like filler in the metal member adhesive composition is preferably in the range of 10% by mass to 40% by mass of the total mass of the metal member adhesive composition. If the content rate of a plate-shaped filler is in said range, shrinkage | contraction of resin by heat | fever will be relieve | moderated and desired adhesiveness and hot water resistance will become favorable. When the content ratio of the plate-like filler is less than 10% by mass, the shrinkage relaxation of the resin due to hot water tends to decrease. Moreover, when the content rate of a plate-shaped filler exceeds 40 mass%, since the resin component which contributes to adhesiveness will decrease, adhesiveness fall will occur easily.

  The thermoplastic resin is used as a base material for the adhesive composition.

  As a thermoplastic resin, an acrylic resin is illustrated, for example. The acrylic resin contains a (meth) acrylic acid ester as a main component, and is obtained by polymerizing a methyl methacrylate monomer, a polyfunctional acrylic monomer, a prepolymer or a polymer.

  Examples of (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, and n (or iso) -propyl (meth) acrylate. Further, n (or iso or tert) -butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate and the like are also exemplified.

  Moreover, the acrylic resin contains the other monomer component copolymerizable with the said (meth) acrylic acid ester as a copolymerizable monomer as needed for the purpose of the improvement of the characteristic of a resin film or a cured film, etc. Also good.

  Examples of the copolymerizable monomer include styrenes such as styrene, α-methylstyrene, and tert-butylstyrene. Examples thereof include unsaturated carboxylic acids such as itaconic acid, fumaric acid, maleic acid and half esters thereof, (meth) acrylamide, N-methylolacrylamide, dimethylaminoethyl (meth) acrylate and the like. Examples include vinyl pyrrolidone, β-hydroxyethyl (meth) acrylate, polyethylene glycol (meth) acrylate and methoxylated products thereof, and hydroxyl group and polar group-containing monomers such as (meth) acrylic acid monoesters of polyhydric alcohols. The In addition, vinyl esters such as vinyl acetate and vinyl versatate, vinyl ethers of various alkyl groups, α-olefins such as ethylene and propylene, halides such as vinyl chloride, vinylidene chloride and vinylidene fluoride, and divinylbenzene Illustrated. Furthermore, diallyl compounds, di (meth) acrylates, tri (meth) acrylates, vinylsilanes and the like are also exemplified.

  A thermoplastic acrylic resin can be prepared by copolymerizing these copolymerizable monomers with (meth) acrylic acid ester. Since the thermoplastic acrylic resin dissolves when heated, when a thermoplastic resin such as a vinyl chloride resin film is used for the top coat, it adheres firmly at the time of molding.

  Examples of such commercially available acrylic resins include A-405, A-430-60, 54-172-60, A-416-70S, A-413-70S, A-1300, A-188, and A. -1370, A-1371 (manufactured by DIC Corporation) and the like. In addition, A-1380, A-1381A-1815, A-181, A-136-55, A-168, A-1711-IM, A-166, A-165, 56-1155, WDL-787, WAL- 578, 57-789-BL (manufactured by DIC Corporation) and the like. Moreover, 57-451, CL-1000, CL-408, WXU-880, BL-616 (made by DIC Corporation) etc. are illustrated. Moreover, KH-LT, KH-CT-865 (made by Hitachi Chemical Co., Ltd.) etc. are illustrated. Moreover, 785-5, L1090F, L1053, L1042, L1092-1, L1044, L1093, L1060 (made by Mitsui Chemicals) etc. are illustrated. These can be used alone or in combination of two or more.

  The compounding quantity of a thermoplastic resin is not specifically limited, For example, the range of 20-100 mass parts is illustrated. If the blending amount of the thermoplastic resin is within the above range, the adhesiveness will be good.

  A thermosetting resin improves the adhesiveness of an adhesive composition more by using together with a thermoplastic resin.

  An example of the thermosetting resin is a phenol resin.

  The phenolic resin adheres firmly to the metal member by reacting the hydroxyl group or the like in the skeleton with a hydroxyl group on the surface of the metal member.

  Examples of the phenol resin include aralkyl type phenol resins such as novolak type phenol resins such as phenol novolak resins, unsubstituted phenol aralkyl resins, biphenylene type phenol aralkyl resins, and naphthol aralkyl resins. Moreover, dicyclopentadiene type phenol resin, such as dicyclopentadiene type phenol novolak resin, dicyclopentadiene type naphthol novolak resin, and triphenylmethane type phenol resin are exemplified. Further, paraxylylene and / or metaxylylene-modified phenol resins, melamine-modified phenol resins, cyclopentadiene-modified phenol resins, phenol resins obtained by copolymerizing two or more of these, and the like are exemplified. Furthermore, a natural resin-modified phenol resin in which a natural resin such as linseed oil or a terpene resin exists in the structure is exemplified. These can be used alone or in combination of two or more.

  Examples of such commercially available phenol resins include TD-773, TD-2610, TD-2635, AH-5600, TD-2620, TD-2645A, and TD-4304 (manufactured by DIC Corporation). The Moreover, 5010, 5030-40K, TD-1090, TD-2640, TD-3130 (made by DIC Corporation) etc. are illustrated. Moreover, 100S, 200N, 1010R, 510, 521, 526, 586, 572S, 7509 (made by Arakawa Chemical Industries, Ltd.), etc. are illustrated. These can be used alone or in combination of two or more.

  Moreover, an epoxy resin can be mixed with a phenol resin as a thermosetting resin.

  Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin, and phenol novolac type epoxy resin. Further, cresol novolac type epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, and phenol aralkyl type epoxy resin are exemplified. Moreover, a naphthol novolak type epoxy resin, a naphthol aralkyl type epoxy resin, a naphthol-phenol co-condensed novolac type epoxy resin, and a naphthol-cresol co-condensed novolac type epoxy resin are exemplified. Furthermore, aromatic hydrocarbon formaldehyde resin modified phenolic resin type epoxy resin, biphenyl modified novolac type epoxy resin and the like are exemplified. These can be used alone or in combination of two or more.

  The epoxy equivalent of these epoxy resins is preferably 100 to 1000 eq / g.

  The epoxy group in the epoxy resin is basically a bifunctional epoxy group, but may be a trifunctional or higher polyfunctional epoxy group. When the number of functional groups is increased, the crosslinking density is improved, the heat resistance is improved, and when the molecular weight is reduced, the viscosity can be lowered.

  Moreover, a catalyst, a crosslinking agent, etc. can be added to an epoxy resin in order to improve the physical property of resin, unless the hot water resistance of a plate-shaped filler is inhibited. Examples of the catalyst include imidazole and tertiary amine. Examples of the crosslinking agent include amine compounds and carboxylic acid-containing acrylic resins.

  The blending amount of the thermosetting resin is not particularly limited, and examples thereof include a range of 20 to 100 parts by mass. When the blending amount of the thermosetting resin is within the above range, the adhesiveness is good.

  About the other component of the adhesive composition for metal members, unless the hot water resistance of a plate-shaped filler is inhibited, it does not restrict | limit. For example, diluting solvent, inorganic filler, pigment component, surfactant, antibacterial agent, antifungal agent, matting agent, antifoaming agent, thickener, antisettling agent, leveling agent, dispersing agent, heat stabilizer, ultraviolet ray Examples include absorbents and wax components.

  Examples of the diluent solvent include xylene, methyl ethyl ketone, ethyl acetate, n-butyl alcohol and other hydrocarbons, ketones, esters, alcohols, water and the like. These can be used alone or in combination of two or more.

  Such an adhesive composition for a metal member is used by coating or the like on the metal member.

  The application amount of the metal member adhesive composition can be set so that, for example, the adhesive thickness before drying is within a range of 3 μm to 30 μm. If the coating amount is within the above range, the metal member adhesive composition can be sufficiently supported on the surface of the metal member, and is effective for improving the adhesiveness, rust prevention, and hot water durability. Become.

  As a coating method, a conventionally known method can be applied. Examples thereof include a flow coater, a roll coater, a curtain coat, a knife coat, a spin coat, a table coat, a sheet coat, a sheet coat, a die coat, and a bar coat. Moreover, the spraying method, the airless spray method, the air spray method, the brush coating, the trowel coating, the dipping method, the pulling method and the like are exemplified. These application methods may be automated or applied manually.

  The thermoplastic resin coating and the metal member are bonded via such an adhesive composition for a metal member to obtain a thermoplastic resin-coated metal member. This thermoplastic resin-coated metal member can exhibit hot water resistance while maintaining adhesion and rust prevention. Hot water resistance has not only immediate effects but also durability.

  As a metal member, a steel plate, a steel pipe, a shape steel, a steel strip, a steel bar etc. are illustrated, for example, Preferably a steel plate is illustrated.

  Examples of the steel plate include a galvanized steel plate, a hot dip galvanized steel plate, a steel plate coated with an alloy such as zinc, aluminum, and magnesium. Among these, the hot dip galvanized steel sheet can be made thicker by galvanization, and therefore has better anticorrosion properties than the coated steel sheet, and is practically preferable.

  Examples of the thermoplastic resin coating include vinyl chloride resin, ABS resin, polyethylene resin, polypropylene resin, and polyethylene terephthalate resin. In particular, a vinyl chloride resin is excellent in water resistance and is practically preferable. Examples of the thermoplastic resin coating include a cured film cured by coating or the like, a molded film, and the like.

  In the case of a cured film, the film thickness is preferably exemplified by a range of 20 μm to 500 μm. As a method for forming the cured film, the thermoplastic resin applied to the surface of the metal member is cured, or the metal member and the thermoplastic resin are extruded to coat the surface of the metal member with the thermoplastic resin. For example, it is cured.

  In the case of a film, a vinyl chloride resin film, an acrylic resin film, a polyethylene film, a polypropylene film, a polyethylene terephthalate film, etc. are illustrated, for example. In particular, a vinyl chloride resin film is excellent in water resistance and is practically preferable.

  The film thickness of the thermoplastic resin film is also preferably exemplified as being in the range of 20 μm to 500 μm.

  Although an Example is shown below, the adhesive composition for metal members of this invention and a thermoplastic resin coating | coated metal member using the same are not limited to an Example.

Example 1
As a thermoplastic resin, acrylic resin (DIC-made A-801, NV50%) is 50 parts by mass, and as a thermosetting resin, phenol resin (DIC-made IF-1200, NV30%) is 30 parts by mass, a plate. 20 parts by mass of magnesium phosphite (LF Bowsei MZP-500, manufactured by Kikuchi Color Co., Ltd.) as an anti-settling agent that is at least one of a modified urea series or an unsaturated polyaminoamide series, 0.5 parts by mass of a salt of amide and a low molecular weight polyester acid (ANTI-TERRA-U {ATU} manufactured by Big Chemie Japan Co., Ltd.) and 20 parts by mass of thinner as a diluent solvent were mixed. To this mixture, beads having a diameter of 2 mm were added as a stirrer, and the mixture was dispersed with a paint shaker at room temperature for 3 hours to obtain an adhesive composition for a metal member. At this time, it was prepared so that the dispersed particle diameter of magnesium phosphite is 50 μm or less and the aspect ratio is in the range of 2-100.

This metal member adhesive composition is obtained by subjecting a hot dip galvanized steel sheet with a plate thickness of 0.5 mm and a coating weight per side of 150 g / m ² to a coating chromate treatment using a bar coder. Was 5 to 10 μm. Then, it baked for 5 minutes in 200 degreeC drying oven, laminated | stacked the vinyl chloride resin film on the surface of the steel plate after cooling, and produced the vinyl chloride resin coated steel plate by press-molding at 200 degreeC. Note that the chromate treatment is a chemical conversion treatment that forms an oxide film by treating chromate on the surface of a steel sheet to improve the adhesion of a paint or an adhesive.
(Example 2)
A vinyl chloride resin-coated steel plate was prepared in the same manner as in Example 1 except that the plate-like filler was changed from magnesium phosphate to aluminum tripolyphosphate (K-WHITE 105 manufactured by Teika Co., Ltd.).
(Example 3)
A vinyl chloride resin-coated steel sheet was produced in the same manner as in Example 1 except that the plate-like filler was changed from magnesium phosphate to mica (A-21S manufactured by Yamaguchi Mica Co., Ltd.).
Example 4
A vinyl chloride resin-coated steel sheet was produced in the same manner as in Example 1 except that the plate-like filler was changed from magnesium phosphate to talc (MS-P, manufactured by Nippon Talc Co., Ltd.).
(Example 5)
As a thermosetting resin, a vinyl chloride resin-coated steel sheet was produced in the same manner as in Example 1 except that 10 parts by mass of an epoxy resin (813 manufactured by Mitsui Chemicals, Inc.) was mixed with 30 parts by mass of the phenol resin.
(Example 6)
A vinyl chloride resin-coated steel sheet was prepared in the same manner as in Example 1 except that the anti-settling agent was changed from 0.5 parts by mass of unsaturated polyaminoamide and low molecular weight polyester acid salt to 0.1 parts by mass of the modified urea solution. did.
(Example 7)
A vinyl chloride resin-coated steel sheet was produced in the same manner as in Example 6 except that the plate-like filler was changed from magnesium phosphate to aluminum tripolyphosphate (K-WHITE 105 manufactured by Teika Co., Ltd.).
(Example 8)
A vinyl chloride resin-coated steel sheet was produced in the same manner as in Example 6 except that the plate-like filler was changed from magnesium phosphate to mica (A-21S manufactured by Yamaguchi Mica Co., Ltd.).
Example 9
A vinyl chloride resin-coated steel plate was produced in the same manner as in Example 6 except that the plate-like filler was changed from magnesium phosphate to talc (MS-P, manufactured by Nippon Talc Co., Ltd.).
(Comparative Example 1)
A vinyl chloride resin-coated steel plate was produced in the same manner as in Example 1 except that neither the plate-like filler nor the anti-settling agent was blended.
(Comparative Example 2)
Except that 20 parts by mass of titanium oxide (MT-200S, manufactured by Teika Co., Ltd.), which is a spherical filler, was not blended and no anti-settling agent was blended, no plate-like filler was blended. Thus, a vinyl chloride resin-coated steel plate was produced.
(Comparative Example 3)
Except that no platy filler was blended, 20 parts by mass of spherical filler silica (Aerosil 200 manufactured by Nippon Aerosil Co., Ltd.) and no anti-settling agent were blended, the same procedure as in Example 1 was performed. A vinyl chloride resin-coated steel sheet was prepared.
(Comparative Example 4)
A vinyl chloride resin-coated steel sheet was prepared in the same manner as in Example 1 except that 0.5 part by mass of fatty acid amide wax (PFA-131 manufactured by Enomoto Kasei Co., Ltd.) was blended as an anti-settling agent.
(Comparative Example 5)
A vinyl chloride resin-coated steel sheet was prepared in the same manner as in Example 1 except that 0.1 part by mass of an unsaturated polycarboxylic acid polymer (BYK-P 104 manufactured by BYK Japan Japan Co., Ltd.) was blended as an anti-settling agent. .

For the vinyl chloride resin-coated steel sheets obtained in the examples and comparative examples, the adhesiveness, hot water resistance, rust resistance and sedimentation resistance were evaluated. The evaluation criteria are as follows.
<Adhesiveness>
Test pieces were cut out from the vinyl chloride resin-coated steel sheets obtained in the examples and comparative examples, tested by the cross-cut method based on JIS K5600, and the adhesion of the vinyl chloride resin film was determined according to the following criteria.
○: The vinyl chloride resin film does not peel off and the adhesiveness is good.
Δ: The vinyl chloride resin film partially peeled off.
X: The vinyl chloride resin film peeled entirely. (Not applicable)
<Heat resistant water>
Test pieces were cut out from the vinyl chloride coated steel sheets obtained in the examples and comparative examples, and the test pieces were immersed in boiling water for 1 hour, and then tested by the cross-cut method based on JIS K5600. Was determined according to the following criteria.
A: The vinyl chloride resin film does not peel at all, and the adhesiveness is good.
○: The vinyl chloride resin film hardly peeled off and the adhesiveness was good.
Δ: The vinyl chloride resin film partially peeled off. (Not applicable)
X: The vinyl chloride resin film peeled entirely.
<Rust prevention>
Test pieces were cut out from the vinyl chloride resin-coated steel sheets obtained in the examples and comparative examples, subjected to a 1,000 hour salt spray test in accordance with JIS Z2371, and the occurrence of rust in the cut surface portion and the cross cut portion of the test pieces was observed. Evaluation was made according to the following criteria.
(Double-circle): The peeling width of a crosscut part is less than 1 mm. No generation of rust from the cut surface or cross-cut portion is observed.
○: The peel width of the crosscut portion is within 1 mm. There is almost no rust generation from the cut surface or cross cut.
(Triangle | delta): The peeling width of a crosscut part is less than 1 mm. Rust generation from the cut surface and the cross cut is slightly observed. (Not applicable)
X: The peeling width of the cross cut part is 1 mm or more. Generation of rust from the cut surface and the cross cut portion is observed.
<Precipitation prevention>
The adhesive compositions for metal members obtained in Examples and Comparative Examples are allowed to stand at room temperature for 1 month, then visually confirmed, stirred using a spatula or a disper, and settling prevention properties of the adhesive compositions for metal members. Was determined according to the following criteria.
○: There is no sediment by visual inspection, or there is some sediment, but it can be redispersed by stirring with a spatula.
Δ: Although there is a slight amount of sediment visually, it can be redispersed by stirring for 3 minutes using a disper.
X: There exists a sediment visually, and even if it stirs for 10 minutes using a disper, a sediment remains.

  The evaluation results are shown in Table 1.

  As shown in Table 1, with respect to Examples 1 to 9 in which a plate-like filler and a modified urea-based or unsaturated polyaminoamide-based anti-settling agent were blended, all had adhesiveness, hot water resistance, and rust resistance. It was confirmed that all of the anti-settling properties were good. In particular, it was confirmed that Examples 1, 2, 5, 6, and 7 in which magnesium phosphite or aluminum tripolyphosphate was blended as a plate-like filler were also excellent in rust prevention.

  However, it was confirmed that Comparative Examples 1 to 3 in which no platy filler was added or titanium oxide and silica that were spherical fillers were blended had good adhesiveness, but inferior in rust prevention and hot water resistance. It was. Moreover, since the spherical filler in the adhesive composition for metal members settles and the re-dispersion is difficult for the comparative examples 2 and 3, it was confirmed that the anti-settling property is inferior. Moreover, although Comparative Example 4 and 5 which mix | blended anti-settling agents other than a modified urea type | system | group or an unsaturated polyaminoamide type | system | group were good in rust prevention property, it was confirmed that it is inferior to hot water resistance.

  From these results, in the adhesive composition for metal members, in order to exhibit excellent hot water resistance while maintaining adhesion and rust prevention, in addition to the plate-like filler, modified urea-based or unsaturated It was confirmed that a polyaminoamide type antisettling agent is an essential component. Moreover, it was confirmed that the thermoplastic resin-coated metal member obtained by bonding the thermoplastic resin coating and the metal member can be obtained by this adhesive composition.

Claims (5)

  An adhesive composition for a metal member for bonding a thermoplastic resin coating and a metal member, the anti-settling agent being at least one of a modified urea type or an unsaturated polyaminoamide type, a plate-like filler, and a heat An adhesive composition for metal members, comprising a plastic resin and a thermosetting resin.   The adhesive composition for a metal member according to claim 1, wherein the thermoplastic resin is an acrylic resin and the thermosetting resin is a phenol resin.   The metal member according to claim 1 or 2, wherein the dispersed particle diameter of the plate-like filler in the adhesive composition for a metal member is 50 µm or less and the aspect ratio is in the range of 2 to 100. Adhesive composition.   4. The plate-like filler is at least one selected from the group consisting of plate-like magnesium phosphate, plate-like aluminum phosphate, and plate-like zinc phosphate. The adhesive composition for metal members as described in 2.   A thermoplastic resin-coated metal member, wherein the thermoplastic resin coating and the metal member are bonded via the adhesive composition for a metal member according to any one of claims 1 to 4.