WO2013080844A1 - プライマー組成物 - Google Patents
プライマー組成物 Download PDFInfo
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- WO2013080844A1 WO2013080844A1 PCT/JP2012/080110 JP2012080110W WO2013080844A1 WO 2013080844 A1 WO2013080844 A1 WO 2013080844A1 JP 2012080110 W JP2012080110 W JP 2012080110W WO 2013080844 A1 WO2013080844 A1 WO 2013080844A1
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- WIPO (PCT)
- Prior art keywords
- epoxy resin
- primer composition
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- primer
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Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/02—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using non-aqueous solutions
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
- C09D163/04—Epoxynovolacs
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/38—Epoxy compounds containing three or more epoxy groups together with di-epoxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
- C08G59/4014—Nitrogen containing compounds
- C08G59/4021—Ureas; Thioureas; Guanidines; Dicyandiamides
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/002—Priming paints
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/66—Additives characterised by particle size
- C09D7/67—Particle size smaller than 100 nm
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
Definitions
- the present invention relates to a primer composition, and more particularly to a novel primer composition that enables strong adhesion of a material with an adhesive by improving the affinity for the adhesive on the surface of various materials.
- metal materials such as stainless steel, ordinary steel, aluminum, aluminum alloy, copper, and galvanized steel are widely used in many fields such as building materials and electronic devices by taking advantage of excellent corrosion resistance and surface appearance.
- metal materials When these metal materials are used as structural materials or various parts, it is often required to join the metal material plates to each other or to join the metal material plates to other parts or members. . In such cases, conventionally, most metal material plates have been joined together by welding.
- an adhesion method using an adhesive has been attracting attention as a method for joining metal materials instead of welding.
- the bonding method using an adhesive has an advantage that the sheet metal processing is not necessary because the surface appearance of the metal material is hardly impaired.
- the surface of a metal material is often covered with a stable oxide film.
- the oxide film of stainless steel is excellent in corrosion resistance, but has a very low affinity with an adhesive and is inferior in adhesive strength. There was a problem. Further, since the water resistance of the bonding interface is lowered in the bonding, there is a problem that when the bonding portion of the metal material is exposed to a high temperature and high humidity atmosphere, the adhesive strength is remarkably lowered in a short period of time.
- the affinity of such a metal material for an adhesive can be improved by previously activating the surface of the metal material with an acid.
- a method of treating the surface of a stainless steel plate with a mixed aqueous solution of sulfuric acid and oxalic acid is known.
- a method is also known in which an aluminum plate or an aluminum alloy plate is immersed in a phosphoric acid aqueous solution or a dichromic acid aqueous solution, or is electrically oxidized at the anode while immersed.
- the method of activating the stainless steel surface by the acid treatment has a problem that smut is generated on the stainless steel surface.
- This smut can be removed by treating the stainless steel surface with a mixed aqueous solution of dichromic acid and sulfuric acid.
- this desmutting treatment generates chromium-containing wastewater, it is strictly limited from the viewpoint of environmental destruction.
- Patent Document 1 describes a method of treating a stainless steel plate using an aqueous phosphate containing an acidic phosphate ester and / or salt thereof and water in order to improve the adhesion of the stainless steel plate.
- Patent Document 2 describes a method for improving the adhesion to a fluorine-based coating film by treating the surface of a normal steel plate or stainless steel with a silane coupling agent.
- Non-Patent Document 1 the treatment with a silane coupling agent having a functional group reactive with an epoxy adhesive may improve the adhesion of stainless steel plates, ordinary steel plates, aluminum plates, aluminum alloy plates, and the like. It is stated. Further, Patent Document 3 describes a primer composition mainly composed of a polyfunctional epoxy resin and a bisphenol A type epoxy resin and containing imidazole as a curing agent.
- a non-patent document 2 proposes a silicon coater treatment as a treatment for imparting stable adhesiveness to the bonding portion of various metal materials even in boiling water.
- Patent Document 3 is inferior in film formability (film-forming property) because the primer composition does not contain a filler. Moreover, since dilution is performed with an organic solvent such as toluene or methyl ethyl ketone in order to ensure the workability of coating, it is necessary to consider air pollution by VOC (Volatile Organic Compounds), which is a major limitation in the manufacturing and use processes. There is a drawback of receiving.
- VOC Volatile Organic Compounds
- Non-Patent Document 1 since the silane coupling agent in Non-Patent Document 1 has a monomer structure, it is difficult to uniformly apply the diluted solution to a soiled practical metal surface. That is, a silane coupling agent adheres firmly to a metal surface free of dirt by, for example, a condensation reaction between an alkoxy group or a silanol group that is a hydrolysis product thereof and a hydroxyl group of an oxide layer on the metal surface. Can do.
- Non-Patent Document 2 is a high-temperature flame process, its application is limited to a small base material.
- the present invention has been made in view of the above-described conventional problems, and is a primer composition capable of forming a primer layer having excellent adhesion and film-forming properties on the surface of various materials that can be bonded with an epoxy adhesive.
- the purpose is to provide goods.
- adhesive strength and adhesion durability equal to or better than chemical treatments such as treatment with acid mixed aqueous solutions and silane coupling agents that have been used in the past, and without solvents. It is an object of the present invention to provide a primer composition having a low environmental load and capable of performing a coating operation with a low viscosity.
- a primer composition provided by the present invention is a primer composition applied to the surface of a material that can be bonded with an epoxy adhesive, and the components of the primer composition include an epoxy resin, It comprises a curing agent, a curing catalyst, and an inorganic oxide filler, and the epoxy resin contains at least a bisphenol A type epoxy resin and a phenol novolac type epoxy resin, the curing agent is dicyandiamide, and the curing catalyst is imidazole.
- the inorganic oxide filler comprises at least 0.5 parts by weight of fumed silica having a hydrophobic surface, a primary particle diameter of 7 to 40 nm, and a specific surface area of 50 to 380 m 2 / g based on a total of 100 parts by weight of the epoxy resin. It is characterized by containing 3 parts by weight and containing no solvent.
- the blending ratio of the phenol novolac type epoxy resin and the bisphenol A type epoxy resin is in the range of 10 parts by weight: 90 parts by weight to 30 parts by weight: 70 parts by weight. Is preferred.
- the amount of the dicyandiamide as the curing agent is in the range of 3 to 25 parts by weight with respect to 100 parts by weight of the total epoxy resin.
- the material that can be bonded with the epoxy adhesive is any one selected from the group consisting of stainless steel, ordinary steel, aluminum, aluminum alloy, copper, and galvanized steel. A kind of metal material is preferable.
- the glass transition temperature of the cured product of the primer composition is preferably 100 ° C. or higher.
- a primer layer having excellent adhesion and film-forming properties can be formed on the surface of various materials, and the affinity for epoxy adhesives in various materials can be increased.
- the material provided with the primer layer is bonded with an epoxy adhesive, it can be bonded with a high adhesive strength equal to or higher than that of a treatment with an acid mixed aqueous solution or a chemical treatment with a silane coupling agent. it can.
- low viscosity suitable for application work can be realized without using a solvent, so there is less environmental burden in the application work, and there is no need to worry about air pollution due to VOCs. It is.
- the primer composition of the present invention comprises an epoxy resin, a curing agent, a curing catalyst, and an inorganic oxide filler as essential components.
- the primer composition is applied to the surface of a metal plate or other metal material member to form a primer layer.
- the metal material mainly targeted by the primer composition of the present invention is not limited by the type and form of the material, and various metal materials such as stainless steel, ordinary steel, aluminum, aluminum alloy, copper, and galvanized steel. It can be suitably applied to plate materials such as, members of other forms, metal parts, and the like.
- plate materials such as, members of other forms, metal parts, and the like.
- a steel plate it can be applied to a cold rolled steel plate or a hot rolled steel plate or the like for ordinary steel, and to various stainless steel plates of martensitic, ferritic and austenitic types for stainless steel.
- the epoxy adhesive used for bonding various materials having a primer layer formed using the primer composition of the present invention may be a one-pack type or a two-pack type. Among these, it is more preferable to use a two-pack type epoxy adhesive that provides a large adhesive strength in industrial applications.
- the epoxy resin that is the main component of the primer composition of the present invention is a combination of a bifunctional bisphenol A type epoxy resin and a polyfunctional (hereinafter, polyfunctional means trifunctional or higher) phenol novolac type epoxy resin. ing.
- the bifunctional bisphenol A type epoxy resin has strong adhesion to the metal surface because of its hydrogen bondability with the metal surface due to its hydroxyl group and flexibility and flexibility due to rotation of intramolecular ether bond.
- this bisphenol A type epoxy resin with a polyfunctional phenol novolac type epoxy resin By blending this bisphenol A type epoxy resin with a polyfunctional phenol novolac type epoxy resin, the crosslink density of the cured product is increased, and heat resistance and mechanical strength are improved. In particular, it is particularly important to obtain a high crosslinking density under severe use conditions such as immersion in boiling water.
- the primer composition of the present invention it is preferable to use a mixture of two or more polyfunctional phenol novolac-type epoxy resins so that the viscosity when actually applied is within a practical range.
- the bisphenol A type epoxy resin and the phenol novolac type epoxy resin used in combination with the epoxy resin contained in the primer composition of the present invention have a blending ratio represented by phenol novolac type epoxy resin: bisphenol A type epoxy resin of 10 parts by weight. : 90 parts by weight to 30 parts by weight: 70 parts by weight is preferably blended.
- the blending amount of the phenol novolac type epoxy resin is less than 10 parts by weight with respect to 100 parts by weight of the total epoxy resin, it is difficult to ensure the boiling water resistance of the primer.
- the compounding amount of the phenol novolac type epoxy resin is more than 30 parts by weight with respect to 100 parts by weight of the total epoxy resin, the degree of cross-linking increases and becomes brittle, and a large stress is generated between the metal material, This is because it is difficult to obtain sufficient adhesiveness.
- Dicyandiamide is used as the epoxy resin curing agent. Dicyandiamide is solid at room temperature and hardly reacts with the epoxy resin. However, when the melting point is exceeded, it liquefies and reacts with the glycidyl group of the epoxy resin to be crosslinked and cured.
- the primer composition of the present invention is composed of a dicyandiamide having such characteristics as a curing agent, and is preliminarily blended with an epoxy resin to form a one-component primer composition having excellent storage stability at room temperature.
- the blending amount of dicyandiamide as the curing agent is preferably in the range of 3 to 25 parts by weight with respect to 100 parts by weight of the total epoxy resin.
- the amount of dicyandiamide is less than 3 parts by weight, the primer composition is not sufficiently cured, and it is difficult to obtain satisfactory boiling-water-resistant adhesiveness. Further, when dicyandiamide is added in an amount of more than 25 parts by weight, the curing agent becomes excessive and the primer composition becomes hard and brittle, which is not preferable.
- imidazole is used as a curing catalyst.
- the selection of the curing catalyst is important because it affects the curing performance and cured product properties of dicyandiamide as the curing agent described above.
- Imidazole is often used as a curing agent for general epoxy resins, but in the present invention, it is used in combination with a curing agent dicyandiamide. Thereby, while lowering
- the glass transition temperature of the cured coating film needs to be 100 ° C. or higher.
- the blending amount of imidazole as the curing catalyst is preferably in the range of 0.5 to 2.0 parts by weight with respect to 100 parts by weight of the epoxy resin. If the amount of imidazole is less than 0.5 parts by weight, an uncured phenomenon is likely to occur. Conversely, if the amount exceeds 2.0 parts by weight, curing proceeds during storage of the primer composition and gelation occurs. This is not preferable because it tends to occur.
- 2-methylimidazole is particularly preferable.
- the primer composition of the present invention has good coating properties and film-forming properties on the metal material surface, and also ensures excellent adhesion of the cured coating film to the metal material surface in harsh environments.
- an inorganic oxide filler is blended.
- the resin viscosity temporarily decreases until curing by heating starts.
- the surface of the metal material with dirt has a low surface free energy, and the surface free energy of the epoxy resin becomes higher.
- the primer film is repelled on the surface of the metal material with dirt and the surface is continuous. There is a risk of being lost.
- fumed silica is used as such an inorganic oxide filler.
- titanium oxide added and blended in a primer composition has strong cohesiveness, and has a drawback that it becomes difficult to apply due to its high viscosity during coating operation.
- the fumed silica used in the present invention has at least a hydrophobic surface, a primary particle diameter of 7 to 40 nm, and a specific surface area of 50 to 380 m 2 / g. This is because when the surface is hydrophobic and the particle size is very small, a repulsive force is generated with a highly polar epoxy resin, the cohesiveness of fumed silica is increased, and the network that causes thixotropy is exhibited. This is because it is easy to form a (network) structure.
- the blending ratio of fumed silica with respect to 100 parts by weight of the total epoxy resin is in the range of 0.5 to 3 parts by weight. If the blending amount is less than 0.5 parts by weight, the effect is not sufficient, and if it exceeds 3 parts by weight, the viscosity becomes too high and coating becomes difficult.
- Patent Document 3 described above describes a known primer composition mainly composed of a bisphenol A type epoxy resin and a polyfunctional epoxy resin, but this primer composition is applied at the time of application by solvent dilution. Workability is ensured. Therefore, for example, when toluene is used as a solvent, handling is troublesome because it is necessary to consider air pollution.
- the viscosity suitable for the coating operation with a bar coater or the like specifically 3 to 7 Pa ⁇ s with only the above-described components without using an organic solvent such as toluene. It can be controlled to the extent.
- the primer composition of the present invention building materials and other structural materials having excellent strength can be obtained by a simple construction in which a metal material is bonded using an adhesive. Moreover, the obtained bonded portion is excellent in moisture resistance at high temperature, and can maintain high adhesive strength for a long period of time even when exposed to a high temperature and high humidity environment such as immersion in boiling water.
- the adhesion part can maintain stable adhesion even under severe use conditions such as in a high-temperature strong acid or strong alkaline aqueous solution, New developments in electrochemical processes are possible. That is, the primer composition of the present invention has very high adhesion stability and cross-linking density of the coating film, and is very useful as an insulating film for metals used in strong acid and strong basic aqueous solutions.
- Example 1 Each of the epoxy resin, curing agent, curing catalyst, and inorganic oxide filler is weighed and mixed using the Excel Auto Homogenizer manufactured by Nippon Seiki Seisakusho Co., Ltd. under the conditions of a rotation speed of 10,000 rpm and a mixing time of 2 minutes. Primer compositions of Samples 1 to 16 having the blending amounts shown in Table 1 below were prepared.
- JER828 (shown as epoxy resin A) manufactured by Mitsubishi Chemical Corporation is used as the bisphenol A type epoxy resin used for the epoxy resin
- JER152 (manufactured by Mitsubishi Chemical Corporation) is used as the phenol novolac epoxy resin
- Epoxy resin B) and JER154 (shown as epoxy resin C) were mixed and used.
- a dicyandiamide curing agent (DICY7) manufactured by Mitsubishi Chemical Corporation was used as the curing agent, and 2-methylimidazole manufactured by Shikoku Kasei Co., Ltd. was used as the curing catalyst.
- RY200S indicated as fumed silica powder A1
- RY50 indicated as fumed silica powder A2
- RY300 indicated as fumed silica powder A3
- fumed silica powder B manufactured by Nippon Aerosil Co., Ltd. was used as the hydrophilic fumed silica.
- the primary particle size and specific surface area of these fumed silicas are RY200S (fumed silica powder A1) 16 nm and 130 m 2 / g, RY50 (fumed silica powder A2) 40 nm and 50 m 2 / g, RY300 ( Fumed silica powder A3) is 7 nm and 300 m 2 / g, and 130 (fumed silica powder B) is 16 nm and 130 m 2 / g.
- silica (HS-05) having an average particle diameter of 3 to 24 ⁇ m manufactured by Kinsei Matech Co., Ltd. and an average particle diameter of 0.1 mm manufactured by Ishihara Sangyo Co., Ltd. are used instead of fumed silica.
- 21 ⁇ m titanium oxide (Typaque CR60) was used.
- sample 9 the silica and titanium oxide were added in addition to the fumed silica.
- the film forming property at the time of application was evaluated, and the adhesion performance when the stainless steel plates were bonded to each other using a two-pack type epoxy adhesive was evaluated. Specifically, a plurality of test pieces having a width of 25 mm and a length of 100 mm were cut out from a stainless steel plate (2B finish) of SUS304 having a plate thickness of 1.2 mm, and these test pieces were degreased by acetone immersion at room temperature for 3 minutes. Thereafter, the primer compositions of Samples 1 to 16 were applied to these test pieces to a thickness of 60 ⁇ m using a bar coater, and cured by heating at 175 ° C. for 45 minutes to form a primer layer. The primer layer thus obtained was visually observed to evaluate the film forming property.
- the bonded portions of the test pieces to which these samples 1 to 17 were bonded were cured at room temperature for 24 hours and further held at 100 ° C. for 1 hour to be completely cured. Thereafter, the initial shear bond strength of the bonded test piece was measured according to JIS K6850. Further, in order to investigate the moisture resistance performance of the bonded portion, the bonded test piece was immersed in boiling water for 7 days, and then the shear bond strength was measured in the same manner as described above.
- Table 2 shows the measurement results of the obtained shear bond strength at the initial stage and after immersion in boiling water together with the evaluation of the film forming property of the primer composition.
- the evaluation of the film-forming property is ⁇ when the primer composition film is uniformly formed on the entire surface of the test piece, and the primer composition film is formed but the film is not formed on more than half of the test piece.
- ⁇ the case where the film of the primer composition was not formed at all and became a water droplet was indicated as “x”.
- the results of measuring the viscosity of the primer compositions of Samples 1 to 16 using a B-type viscometer at 40 ° C. and 5 rpm are also shown.
- each of the primer compositions of Samples 1 to 11 according to the present invention has a good film forming property, and at the same time has a high adhesive strength when bonded with an epoxy adhesive, and is excellent. High adhesion strength could be maintained by having water resistance. Moreover, it can be seen from the results of Sample 9 that the viscosity can be kept low even when fumed silica is added with silica powder and titanium oxide, and the film-forming property is good.
- samples 12 to 17 as comparative examples have insufficient film-forming properties or adhesive strength, and in particular, samples 12, 14, 15, and 16 did not form a film, so the adhesion evaluation of the film could not be performed.
- the initial shear bond strength was high, but the shear bond strength was greatly reduced after immersion in boiling water. From these results, bisphenol A type epoxy resin and polyfunctional phenol novolac epoxy resin are properly blended, and hydrophobic fumed silica is added to the system of dicyandiamide curing agent and imidazole catalyst to reduce the viscosity at the time of coating. It can be seen that sufficient film-forming properties and high adhesiveness are maintained while lowering.
- Example 2 In the same manner as in Example 1 except that a test piece cut out from another metal material was used in place of the stainless steel plate, the film forming property and epoxy at the time of application for the primer compositions of Samples 1 to 16 shown in Table 1 above The adhesion performance when the plates were adhered to each other using an adhesive was evaluated, and the adhesion performance in the case of no sample 17 as a sample 17 was evaluated. The results are shown in Table 3 below (when the test piece is a galvanized steel plate), Table 4 below (when the test piece is a copper plate), Table 5 (when the test piece is an aluminum plate), and Table 6 (test piece). Is a normal steel plate).
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Abstract
Description
エポキシ樹脂、硬化剤、硬化触媒、及び無機酸化物フィラーをそれぞれ秤量し、(株)日本精機製作所製のエクセルオートホモジナイザーを用いて、回転数10000rpm、混合時間2分間の条件で混合することにより、下記表1に示す配合量を有する試料1~16のプライマー組成物を調製した。
ステンレス鋼板に代えて他の金属材料から切り出した試験片を用いた以外は上記実施例1と同様にして、上記表1に示す試料1~16のプライマー組成物について塗布時の造膜性及びエポキシ系接着剤を用いて板同士を接着した時の接着性能の評価を行い、さらに試料17としてプライマー層のない場合の接着性能の評価を行った。その結果を、それぞれ下記表3(試験片が亜鉛めっき鋼板の場合)、下記表4(試験片が銅板の場合)、下記表5(試験片がアルミニウム板の場合)、下記表6(試験片が普通鋼板の場合)に示す。
Claims (5)
- エポキシ系接着剤で接着され得る材料の表面に塗布されるプライマー組成物であって、プライマー組成物の成分は、エポキシ樹脂と、硬化剤と、硬化触媒と、無機酸化物フィラーとからなり、該エポキシ樹脂は少なくともビスフェノールA型エポキシ樹脂とフェノールノボラック型エポキシ樹脂とを含み、該硬化剤はジシアンジアミドであり、該硬化触媒はイミダゾールであり、該無機酸化物フィラーは、少なくとも表面が疎水性で一次粒子径7~40nm、比表面積50~380m2/gのフュームドシリカをエポキシ樹脂の合計100重量部に対し0.5~3重量部含有し、溶剤を含有しないことを特徴とするプライマー組成物。
- 前記フェノールノボラック型エポキシ樹脂と前記ビスフェノールA型エポキシ樹脂との配合比が、10重量部:90重量部~30重量部:70重量部の範囲内であることを特徴とする、請求項1に記載のプライマー組成物。
- 前記硬化剤のジシアンジアミドの配合量が、前記エポキシ樹脂の合計100重量部に対し3~25重量部の範囲内であることを特徴とする、請求項1に記載のプライマー組成物。
- 前記材料は、ステンレス鋼材、普通鋼材、アルミニウム材、アルミニウム合金材、銅材、及び亜鉛めっき鋼材の群から選ばれるいずれか一種であることを特徴とする、請求項1に記載のプライマー組成物。
- 前記プライマー組成物の硬化物のガラス転移温度が100℃以上であることを特徴とする、請求項1から4のいずれかに記載のプライマー組成物。
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US14/361,485 US9057132B2 (en) | 2011-11-30 | 2012-11-20 | Primer composition |
CN201280068477.2A CN104080866B (zh) | 2011-11-30 | 2012-11-20 | 底漆组合物 |
CA2857309A CA2857309C (en) | 2011-11-30 | 2012-11-20 | Primer composition |
EP12854195.0A EP2789660A4 (en) | 2011-11-30 | 2012-11-20 | PRIMER COMPOSITION |
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CN103665775A (zh) * | 2013-11-21 | 2014-03-26 | 无锡创达电子有限公司 | 一种硅微粉高填充的环氧模塑料及其制备方法 |
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JP6060880B2 (ja) * | 2013-11-28 | 2017-01-18 | 住友金属鉱山株式会社 | プライマー組成物 |
GB201514516D0 (en) * | 2015-08-14 | 2015-09-30 | Cytec Ind Inc | Fast-cure pre-preg |
JP6551366B2 (ja) * | 2016-10-31 | 2019-07-31 | Jfeスチール株式会社 | ポリエチレン被覆鋼管及びその製造方法 |
US11466180B2 (en) * | 2017-05-08 | 2022-10-11 | Avery Dennison Corporation | Vulcanization tire label |
JP7360025B2 (ja) * | 2019-08-30 | 2023-10-12 | 日本製鉄株式会社 | 複合体およびその製造方法、ならびに塗装金属板 |
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EP2789660A1 (en) | 2014-10-15 |
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EP2789660A4 (en) | 2015-08-19 |
CN104080866A (zh) | 2014-10-01 |
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