Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
• • 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
  • C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
  • C09D123/02—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
• • 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
  • C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
  • C09D123/02—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
  • C09D123/04—Homopolymers or copolymers of ethene
  • C09D123/08—Copolymers of ethene
  • C09D123/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
  • C09D123/0869—Acids or derivatives thereof
• • 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
  • C09D5/03—Powdery paints
  • C09D5/033—Powdery paints characterised by the additives
• • 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
  • C08K5/00—Use of organic ingredients
  • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
  • C08K5/0041—Optical brightening agents, organic pigments
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/04—Homopolymers or copolymers of ethene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31511—Of epoxy ether

Definitions

• the present invention relates to a coating composition that imparts chipping resistance and a vehicle body component to which the coating composition is applied.
• a coating film obtained by curing a coating composition is provided on a component on the side close to a road surface, for example, a lower surface of a floor panel or a drive shaft.
• This coating film protects the site where the coating film is provided and avoids scratches when pebbles or gravel bounced up by a tire collides with the vehicle while it is running.
• the coating film functions as a protective film, and for this reason, resistance (chipbing resistance) when pebbles or gravel collides is desired.
• an epoxy resin-based coating composition mainly composed of epoxy resin that adheres firmly to a work and has excellent antifouling power is widely used.
• the epoxy resin composition has a disadvantage that it has a relatively high glass transition point and thus is brittle in cold districts and the like, so that it is not easy to ensure the chipping resistance and the water absorption is also relatively high. .
• Patent Document 1 a powder coating comprising a solid powder containing an olefin-based resin, a solid powder containing a polar group-containing modified olefin-based resin, and a solid powder containing an epoxy resin.
• a composition is proposed! RU When this powder coating composition is used, a multilayer coating film having a cured epoxy resin as a lower layer and an olefin-based resin film as a surface layer is formed.
• Patent Documents 2 and 3 a coating having a bottom layer that also has an epoxy powder coating power, an intermediate layer that also has an adhesive polyolefin linker having a polar group, and a top layer that also has a polyolefin linker is provided on the steel pile. It is described that it is provided on the outer surface.
• Patent Documents 4 and 5 also propose providing a coating film in which an epoxy powder coating and a polyolefin resin are laminated or semi-interpenetrated.
• Patent Document 1 Japanese Patent Publication No. 62-27109
• Patent Document 2 Japanese Patent Laid-Open No. 2-8043
• Patent Document 3 Japanese Patent Laid-Open No. 63-258680
• Patent Document 4 Japanese Patent Publication No. 11 513416
• Patent Document 5 Japanese Patent Publication No. 62 27109
• a main object of the present invention is to provide a coating composition having good chipping resistance under a low temperature environment.
• Another object of the present invention is to provide an automobile body constituting member to which the coating composition is applied.
• an epoxy resin powder coating material an epoxy resin powder coating material
• the polyolefin resin or the polar group-containing modified olefin fin resin has a melt index at 190 ° C of 0.1 to 80 gZlO min, an embrittlement temperature of 100 ° C to 20 ° C, and the epoxy resin.
• a coating composition is provided in which the powdered fat coating is 1 to 70 parts by weight and at least one of the polyolefin resin or the polar group-containing modified olefin fin resin is 99 to 30 parts by weight.
• an epoxy resin powder coating material and at least one of a polyolefin resin and a polar group-containing modified olefin resin that can physically bind to epoxy resin are used.
• the paint composition is blended.
• the coating composition is derived from epoxy resin and exhibits a strong adhesion to the workpiece, as well as excellent corrosion resistance and water resistance.
• Also derived from polyolefin resin or polar group-containing modified olefin fin resin Thus, even in a low temperature environment, good chipping resistance is exhibited.
• a coating film that adheres firmly to a workpiece and exhibits excellent corrosion resistance, water resistance, and chipping resistance is obtained, whereby a workpiece on which the coating film is formed is obtained. Protected to improve durability.
• affinity is defined as a property in which different types of materials attract each other physically and Z or chemically, and examples thereof include hydrogen bonding and binding by van der Waalska. Is mentioned.
• a carboxyl group-containing modified olefin fin resin one having a carboxyl group as a polar group can be mentioned.
• a polar group can be introduced by copolymerizing a carboxyl group-containing bulle monomer, an unsaturated carboxylic acid or an anhydride thereof, or by graft polymerization.
• Specific examples of this type of polar substance include acrylic acid, methacrylic acid, vinyl acetate, maleic anhydride, maleic acid and the like.
• the epoxy resin contained in the epoxy resin powder coating material preferably has a softening point of 30 ° C. to 160 ° C. In this case, it is excellent in handling at room temperature and the kneading of the epoxy resin powder coating material becomes easy.
• the epoxy resin powder coating material is 1 to 70 parts by weight, and at least one of polyolefin resin or polar group-containing modified olefin fin resin is 99 to 99 parts.
• a coating film obtained by curing the coating composition in a proportion of 30 parts by weight is provided,
• the polyolefin resin or the polar group-containing modified olefin fin resin has a melt index of 0.1 to 80 gZlO min at 190 ° C and an embrittlement temperature of -100 ° C to 120 ° C.
• the group-containing modified olefin fin resin provides an automobile body component having a polar group having an affinity for epoxy resin.
• the automobile body constituting member having such a configuration is protected by the coating film even if pebbles, gravel, or the like collides. For this reason, it is avoided that a damage
• this coating film has good corrosion resistance and water resistance, generation of wrinkles on the automobile body component is also suppressed. Eventually, the automobile body component is less likely to be scratched or wrinkled even in a low temperature environment.
• the automobile body component is not particularly limited, the floor panel, the drive A shaft or various types of panel (for example, a panel constituting a suspension) can be cited as a suitable example.
• examples of the polar group-containing modified olefin fin resin include those having a carboxyl group as a polar group.
• the epoxy resin contained in the epoxy resin powder coating material preferably has a softening point of 30 ° C to 160 ° C.
• FIG. 1 is a system outline diagram of a power transmission mechanism incorporating a drive shaft provided with a coating film made of a coating composition according to the present embodiment.
• FIG. 2 is a chart comparing various physical properties of the coating films of Examples 1 to 4 and Comparative Examples 1 and 2.
• FIG. 10 a driving force transmission mechanism for transmitting driving force from the engine to the tire is shown in FIG.
• a half shaft 14 and spline shafts 16a and 16b are connected in order from the differential gear 12, and the spline shafts 16a and 16b are connected to a hub (not shown). ).
• the rotary shaft 18 of the half shaft 14 or the differential gear 12 and the spline shafts 16a and 16b are connected via a triport type constant velocity joints 20a and 20b, while the spline shafts 16a and 16b and the hub are connected to each other. Are connected via barfield type constant velocity joints 22a and 22b. Therefore, the rotational driving force from the engine is the differential gear 12, the triport type constant velocity joints 20a, 20b, the half shaft 14 or the rotary shaft 18, the spline shafts 16a, 16b, the barfield type constant velocity joints 22a, 22b, And transmitted to the tire (not shown) via the hub.
• a coating film is formed on the surface of the half shaft 14 and the spline shafts 16a and 16b, that is, the drive shaft.
• This coating film comprises at least epoxy resin powder paint and polyolefin resin or polar group-containing modified olefin resin.
• the coating composition in which either one is blended is formed by curing.
• the epoxy resin powder coating material contains an epoxy resin, a curing agent, a pigment, and various additives.
• the epoxy resin those having an epoxy equivalent of 170-2100 g / eq are preferred, and those having an epoxy equivalent of 600-1200 gZeq are preferred.
• the epoxy resin preferably has a soft point of 30 ° C to 160 ° C.
• the softening point is less than 30 ° C, it is difficult to maintain a solid state at room temperature, and thus it is not easy to make a powder coating. If it exceeds 160 ° C, it will not soften easily during the kneading process described later.
• An epoxy resin having a soft softness point of 50 ° C to 150 ° C is more preferable, and an epoxy resin having a softness point of 60 ° C to 140 ° C is more preferable.
• Such an epoxy resin includes Epicoat 1004 (trade name made by Japan Epoxy), Epototo YDO 14 (trade name made by Tohto Kasei), Epiclon 4050 (product made by Dainippon Ink & Chemicals, Inc.) Name) etc., and can be easily obtained as a commercial product.
• the curing agent is not particularly limited as long as it is a substance capable of curing epoxy resin, but it has ammine, amidine, acid anhydride, phenol having novolac structure, and bisphenol type epoxy as a skeleton.
• Preferable examples include phenol, diaminodiphenylmethane (DDM), adipic acid dihydrazide (ADH), and substances obtained by adding imidazoles thereto.
• the ratio of the curing agent is sufficient to be 1 to 20% by weight when the total weight of the epoxy resin powder coating is 100% by weight.
• Examples of the pigment include those generally used as a pigment.
• titanium oxide as a coloring pigment
• petal yellow iron oxide such as ocher, carbon black, quinatalidone, azo compound, metal complexes such as dioxane, selenium, phthalocyanine, and various metal salts.
• extender pigments include barium sulfate, silicon dioxide, talc, calcium carbonate, potassium titanate whisker, aluminum borate whisker, wollastonite, aluminum oxide, and other ceramic powders.
• Pigment is not an essential component! / ⁇ is added, but when added, the total weight of the epoxy resin powder coating is 100% by weight, preferably 1 to 80% by weight 10 ⁇ 80% by weight is more preferred!
• Leveling agents, waxes, defoaming agents, antioxidants, UV absorbers, and the like are added as additives. Additives are not an essential component, but when added, when the total weight of the epoxy resin powder coating is 100% by weight, 0.1 to LO weight% is preferred 0.3 to More preferably, it is 7% by weight.
• the polyolefin resin on the other hand, one having a melt index of 0.1 to 80 gZlO at 190 ° C. is selected from those polymerized using olefin as a monomer. If the melt index is less than 0.1 lgZlO, sufficient fluidity will not be exhibited during baking after coating, making it difficult to obtain a smooth coating film. On the other hand, when the content exceeds 80 gZlO, the repelling property is improved, but the brittle temperature is increased, so that the chipping resistance in a low temperature environment is lowered. Polyolefin resin having a melt index of 0.15 to 50 gZlO is more preferable. Polyolefin resin having a melt index of 0.2 to 30 gZlO is more preferable.
• the polyolefin resin one having a brittle temperature of 1100 ° C to 20 ° C is selected. If the brittle temperature exceeds 20 ° C, the chipping resistance in a low temperature environment is not sufficient. If it is less than 100 ° C, it is difficult to grind.
• a polar group-containing modified olefin resin may be blended.
• the polyolefin resin and the polar group-containing modified polyolefin resin may be blended at the same time.
• the polar group-containing modified olefin fin resin has a melt index at 190 ° C of 0.1 to 80 gZlO and a brittle temperature of 100 ° C to 20 ° C. Is selected. The reason is as described above.
• the polar group of the polar group-containing modified olefin fin resin is a functional group having an affinity for styrene resin, and specifically, a carboxyl group is exemplified.
• Preferred examples of the polar group-containing modified olefin fin resin having such a functional group include Admer, UM1420, and Flowen 13142.
• Admer is a product name of low-density polyethylene resin manufactured by Mitsui Engineering Co., Ltd., which has a melt index at 190 ° C of 9g / 10min and an embrittlement temperature of -60 ° C or less.
• UM1420 and Flocene 13142 are trade names of low-density polyethylene resin for fluid immersion manufactured by Ube Industries and low-density polyethylene resin for electrostatic coating manufactured by Sumitomo Seika Co., Ltd. at 190 ° C.
• the melt index is 20g / 10min, lOgZl 0 minutes, the embrittlement temperature is 70 ° C or less and -80 ° C or less.
• the polyolefin resin or the polar group-containing modified olefin fin resin may be colored with carbon black or the like.
• the weight ratio of the epoxy resin powder coating material and the polyolefin resin or the polar group-containing modified olefin resin is set to 1 to 70:99 to 30.
• the ratio of polyolefin resin or polar group-containing modified olefin resin is less than 30 parts by weight
• Chipping resistance near 40 ° C is not sufficient. On the other hand, when it exceeds 99 parts by weight, it is difficult to provide a coating film having a uniform surface state.
• the coating film is provided as follows from a coating composition containing such components.
• an epoxy resin powder coating is prepared. That is, the above-described epoxy resin, hardener, and additives are mixed at room temperature and kneaded using a kneader generally used for producing powder coating materials such as a uniaxial or biaxial extruder.
• the pellets thus formed are pulverized with a pulverizer such as pin mill to form, for example, a powder having a particle size of 200 m or less, and the particle size distribution of the powder is set within a predetermined range using a sieve or the like.
• the polyolefin resin, the polar group-containing modified olefin resin, or a mixture thereof is pulverized at room temperature or below freezing to obtain a powder having a particle size of 300 m or less, for example.
• This powder may also have a particle size distribution within a predetermined range with a sieve or the like.
• Each powder obtained as described above was prepared in an amount of 1 to 70 parts by weight of an epoxy resin powder coating material, and 99 to 30 parts by weight of at least one of polyolefin resin or polar group-containing modified olefin resin. If it mix
• the coating is applied to the nozzle shaft 14 and spline shafts 16a and 16b by electrostatic coating, fluid immersion, in-mold, etc., and then in a hot air furnace, an infrared furnace, or an induction heating furnace.
• the coating composition can be provided by baking.
• phase separation between the epoxy resin powder coating material and the polyolefin resin or polar group-containing modified olefin resin occurs in the coating composition.
• the coating film thus provided is derived from epoxy resin and adheres firmly to the work (half shaft 14 and spline shafts 16a, 16b) and has excellent corrosion resistance.
• it is derived from polyolefin resin or polar group-containing modified olefin fin resin, and exhibits good chipping resistance even in a low temperature environment.
• the automobile body component on which the coating film is formed is not particularly limited to the half shaft 14 or the spline shafts 16a and 16b, and may be a floor panel (not shown). Well, it ’s the panel that makes up the suspension!
• the workpiece to which the coating composition is applied is not particularly limited to the automobile body constituent member! /.
• Epiclon 4050 (trade name, manufactured by Dainippon Ink and Chemicals, Epoxy equivalent: 945 g / eq, soft point: 100 ° C), 100 parts by weight, ADH, a hardener, 6 parts by weight, 20 parts by weight of barium sulfate, 1.5 parts by weight of carbon black, and 2 parts by weight of BYK360P, an acrylic leveling agent, were premixed with a high-speed mixer, and then kneaded, pulverized, and classified to obtain an average particle An epoxy resin powder coating material having a diameter of 50 ⁇ m was obtained.
• Admer NS 101 marketed as a powder with an average particle size of 180 ⁇ m, was used.
• both powders were blended in the proportions shown in Fig. 2 to obtain a coating composition.
• This coating composition was electrostatically applied to a mild steel plate (sheet thickness 6 mm) blasted blasted and kept at 180 ° C for 20 minutes to be cured. As a result, a smooth coating film having a thickness of about 100 m was obtained.
• a mild steel plate sheet thickness 6 mm
• sheet thickness 6 mm sheet thickness 6 mm
• the corrosion resistance was sprayed with salt water on the coating film in which an X-shaped cut was previously made in accordance with JIS K 5600 7-1, and after 500 hours, the tape was pressed and peeled off.
• the evaluation was based on whether or not the coating film had peeling. If the peel width from the notch is within 1 mm, “ ⁇ ” is indicated, and if further peeling occurs, “X” is indicated.
• ⁇ indicates that the coating film is smooth and the adhesion is 100Z100
• X indicates that the coating film is not smooth and a large number of recesses are generated in the cross-cut adhesion test. It was.
• the coating film provided only with Admer NS 101 had many pinholes and was poor in appearance.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
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• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Wood Science & Technology (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Paints Or Removers (AREA)
• Motor Power Transmission Devices (AREA)

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• 2004
  • 2004-12-28 JP JP2004379991A patent/JP2006182963A/ja active Pending
• 2005
  • 2005-12-28 US US11/794,350 patent/US20080102283A1/en not_active Abandoned
  • 2005-12-28 WO PCT/JP2005/024139 patent/WO2006070887A1/ja not_active Ceased

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