WO2022145376A1 - Composition de revêtement de peinture primaire durcissable par rayonnement actinique pour plastique renforcé de fibres - Google Patents

Composition de revêtement de peinture primaire durcissable par rayonnement actinique pour plastique renforcé de fibres Download PDF

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WO2022145376A1
WO2022145376A1 PCT/JP2021/048273 JP2021048273W WO2022145376A1 WO 2022145376 A1 WO2022145376 A1 WO 2022145376A1 JP 2021048273 W JP2021048273 W JP 2021048273W WO 2022145376 A1 WO2022145376 A1 WO 2022145376A1
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oil
meth
alkyd resin
active energy
modified alkyd
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PCT/JP2021/048273
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English (en)
Japanese (ja)
Inventor
貴博 荒木
英明 奥田
順子 水口
大嗣 馬野
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日本ペイント・オートモーティブコーティングス株式会社
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Publication of WO2022145376A1 publication Critical patent/WO2022145376A1/fr

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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
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/08—Polyesters modified with higher fatty oils or their acids, or with natural resins or resin acids
    • 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
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • 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
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic

Definitions

  • the present invention relates to an active energy ray-curable undercoat coating composition for FRP that performs metal vapor deposition.
  • Reflector members such as automobile lighting fixtures are made of fiber reinforced plastics such as unsaturated polyester resin (BMC: bulk molding compound) reinforced with fillers such as glass fiber from the viewpoint of being lightweight and having excellent corrosion resistance, heat resistance, and impact resistance.
  • BMC unsaturated polyester resin
  • FRP also referred to as "FRP"
  • FRP fiber reinforced plastics
  • a method of forming a mirror surface on FRP a method of vapor deposition or sputtering of a metal such as aluminum is generally used, but it is difficult to obtain a smooth material surface due to segregation of fibers or mixed air bubbles, and it is usually on the FRP surface.
  • a method is adopted in which a mirror surface is obtained by depositing a metal after the undercoat paint is applied and cured.
  • the undercoat paint used for this purpose has heat resistance to light bulbs, engines, sunlight, etc., as well as heat sources that melt metals in vacuum deposition and sputtering processes, and metals that collide with and adhere to coatings at high temperatures. Heat resistance is also required, and active energy ray-curable paints having excellent coating film hardness have been used.
  • the above-mentioned undercoat paint has been formulated with an oil-modified alkyd resin having excellent corrosion resistance, heat resistance, and repeated cold heat resistance, which achieves both adhesion to the non-uniform material surface where fibers are segregated and adhesion to vapor-deposited metal.
  • the oil-modified alkyd resin is produced by a dehydration condensation reaction between a monofunctional fatty acid such as soybean oil, a bifunctional or higher acid such as phthalic acid or an acid anhydride thereof, and a bifunctional or higher alcohol such as ethylene glycol.
  • the solvent used for the dehydration condensation reaction is required to have a low meltability of water and a boiling point suitable for the dehydration condensation reaction temperature, and xylene (a mixture of ortho-type, meta-type, para-type and ethylbenzene) has been generally used. rice field.
  • xylene can be used as thinner for paints, it can be used without removing the solvent or replacing the solvent.
  • xylene has an effect on the human body and aquatic organisms as a harmful substance along with benzene and toluene, and in recent years, the scope of application of paints containing a certain amount or more of xylene has been severely restricted. Attempts have been made to produce an alkyd resin using a xylene substitute solvent, but since the substitute solvent is not suitable for paint thinner, the painting workability and the appearance of painting are deteriorated. Further, desolvation of xylene has been tried, but there are problems that the energy required for desolvation is large, the stability of the alkyd resin after desolvation is deteriorated, and the storage stability is deteriorated. Active energy ray-curable undercoat paint compositions for FRP that perform metal vapor deposition without using alkyd resin are also being developed, but the material selectivity for the reflector member of automobile lamps, which is a combination of various materials, is The width is narrow.
  • Filaments and HID-type light bulbs used in conventional automobile lamps generate a large amount of heat as light is generated, so even if water gets inside the lamp due to rain or car wash, the internal space is dry due to the use of the lamp. ..
  • an LED bulb that does not generate heat in the light radiation direction the moisture in the space inside the lamp cannot be removed, so that the moisture resistance of the coating film is required to be improved.
  • the 2020 automobile catalog there are no automobiles that use filaments or HID bulbs, and they are mostly LED bulbs.
  • Patent Document 1 (WO 1995/032250) describes an ultraviolet curable undercoat liquid composition for metal vapor deposition for FRP containing a compound having at least two (meth) acryloyl groups and an oil-modified alkyd resin.
  • xylene is essential as a diluent in this composition, it cannot be used in applications that limit the use of xylene.
  • the composition using the alkyd resin of Patent Document 1 is applied to an automobile lamp fixture reflective member for LED bulbs, it contains a large amount of xylene having a high boiling point. Whitening due to poor drying and defective mirror surface after vapor deposition are likely to occur in thick film areas.
  • the present invention improves the undercoat coating composition of Patent Document 1, uses almost no xylene as a solvent, improves dryness and moisture resistance, and provides an undercoat coating for an automobile lighting fixture reflective member corresponding to an LED light bulb. It is an object of the present invention to provide a composition that can be used.
  • An active energy ray-curable undercoat coating composition for FRP which comprises metal vapor deposition containing a polyfunctional (meth) acrylate (A) and an oil-modified alkyd resin (B).
  • the polyfunctional (meth) acrylate (A) has four or more (meth) acryloyl groups in the molecule, and the total amount of the polyfunctional (meth) acrylate (A) and the oil-modified alkyd resin (B). It is contained in an amount of 25 to 45 parts by mass with respect to 100 parts by mass.
  • the oil-modified alkyd resin (B) is contained in an amount of 55 to 75 parts by mass with respect to 100 parts by mass of the total amount of the polyfunctional (meth) acrylate (A) and the oil-modified alkyd resin (B).
  • the oil-modified alkyd resin (B) has an oil length of 35 to 50%, an acid value of 0.01 to 10 mgKOH / g, a hydroxyl value of 80 to 130 mgKOH / g, and a weight average molecular weight of 80,000 to 150,000.
  • Active energy ray-curable undercoat coating composition for FRP Active energy ray-curable undercoat coating composition for FRP.
  • the oil-modified alkyd resin (B) is modified by at least one selected from the group consisting of tall oil, soybean oil, safflower oil, flaxseed oil, millet oil, castor oil and a mixture of these fats and oils.
  • the active energy ray-curable undercoat coating composition for FRP which comprises the metal vapor deposition according to [1].
  • the oil / fat component (b) used for the modification of the oil-modified alkyd resin (B) has an iodine value of 80 to 160 when used alone or in a mixture of two or more kinds of oils and fats, [1] or [2].
  • the active energy ray-curable undercoat coating composition for FRP which performs metal deposition according to the above.
  • the active energy ray-curable undercoat coating composition further contains a photopolymerization initiator (C) in an amount of 1 to 15 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B).
  • the active energy ray-curable undercoat coating composition for FRP which performs the metal deposition according to any one of [1] to [3].
  • the active energy ray-curable undercoat coating composition is at least one selected from the group consisting of a surface conditioner, an ultraviolet absorber, a light stabilizer, an antioxidant, a storage stabilizer, an adhesion imparting agent and a mixture thereof.
  • the active energy ray-curable undercoat coating composition for FRP which comprises a seed and is subjected to the metal deposition according to any one of [1] to [4].
  • the active energy ray-curable primer composition further comprises at least one selected from the group consisting of organic pigments, inorganic pigments, organic beads, inorganic beads and mixtures thereof, according to [1] to [5].
  • the active energy ray-curable undercoat coating composition for FRP which carries out the metal vapor deposition according to any one.
  • the present invention provides an active energy ray-curable undercoat coating composition for FRP that performs metal vapor deposition excellent in storage stability and coating appearance even if the xylene content in the coating material is less than 1%.
  • the oil-modified alkyd resin is adjusted to have an oil length of 35 to 50%, an acid value of 0.01 to 10 mgKOH / g, a hydroxyl value of 80 to 130 mgKOH / g, and a weight average molecular weight of 80,000 to 150,000. It has become possible to significantly reduce the content of xylene.
  • the present invention includes improvement of moisture resistance and xylene as much as possible from the viewpoints of adhesion of a difficult-to-adhere material (specifically, unsaturated polyester resin) to a reflective member of an automobile lamp, energy saving, environmental friendliness, and compatibility with LED bulbs. It relates to an active energy ray-curable undercoat coating composition for FRP, which is subjected to metal vapor deposition using a non-alkyd resin.
  • the active energy ray-curable undercoat coating material for FRP is an active energy ray-curable undercoat coating composition containing a polyfunctional (meth) acrylate (A) and an oil-modified alkyd resin (B), and is a polyfunctional (meth) acrylate.
  • A has four or more (meth) acryloyl groups in the molecule, and with respect to 100 parts by mass of the total amount of the polyfunctional (meth) acrylate (A) and the oil-modified alkyd resin (B).
  • the oil-modified alkyd resin (B) is contained in an amount of 100 parts by mass with respect to the total amount of the polyfunctional (meth) acrylate (A) and the oil-modified alkyd resin (B).
  • the oil-modified alkyd resin (B) contained in an amount of 55 to 75 parts by mass has an oil length of 35 to 50%, an acid value of 0.01 to 10 mgKOH / g, a hydroxyl value of 80 to 160 mgKOH / g, and a weight average molecular weight. It has 80,000 to 150,000.
  • the component (A) of the active energy ray-curable paint undercoat coating composition of the present invention is a polyfunctional (meth) acrylate having at least four (meth) acryloyl groups in the molecule. It is necessary to have "at least 4" (meth) acryloyl groups, but for example, in the case of a compound synthesized by the dehydration reaction of polyhydric alcohol and acrylic acid, the average number of (meth) acryloyl groups per molecule is 3 .5 or more can be considered as a tetrafunctional polyfunctional (meth) acrylate and used.
  • the polyfunctional (meth) acrylate is polymerized by the action of a photopolymerization initiator by irradiation with ultraviolet rays and cured to form an undercoat coating film.
  • the polyfunctional (meth) acrylate (A) is specifically obtained by reacting (a) a polyol having at least four or more hydroxyl groups with (meth) acrylic acid, and (b) a molecule.
  • examples thereof include urethane acrylate obtained by adding a compound having a hydroxyl group and a (meth) acryloyl group to a compound having at least four terminal isocyanet groups.
  • Polyfunctional (meth) acrylate (A) It can be prepared by dealcolytic reaction of a polyhydric alcohol having at least 4 hydroxyl groups and a (meth) acrylate, and as a specific example of the polyfunctional (meth) acrylate (A), for example, average functionality
  • ditrimethylol propanetetra (meth) acrylate ditrimethylol propanetetra (meth) acrylate; a mixture of tritrimethylol propanetetra (meth) acrylate and trimethylol propanepenta (meth) acrylate having an average number of functional groups of 4.0 or more; Dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate mixture, dipentaerythritol penta (meth) acrylate, dipentaerythritol having an average number of functional groups of 5.5 or more.
  • Examples thereof include a mixture of hexa (meth) acrylates, dipentaerythritol penta (meth) acrylates, dipentaerythritol hexa (meth) acrylates; tripentaerythritol (meth) acrylates having an average number of functional groups of 6.5 or more.
  • One of these polyfunctional (meth) acrylates (A) may be used alone, or two or more thereof may be mixed and used.
  • the hydroxyl group-containing (meth) acrylate compound include hydroxyethyl (meth) acrylate, glycerindi (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, and trimethylolpropane tri (meth) acrylate. , Dipentaerythritol penta (meth) acrylate and the like.
  • Examples of the isocyanate compound having at least four isocyanate groups in the molecule include isophorone diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, norbornan diisocyanate, and 1,3-bis (isocyanato). Examples thereof include methyl) cyclohexane (cis-, trans-mixed) and nurate-type trimers thereof.
  • urethane (meth) acrylate (A) a hydroxyl group-containing (meth) acrylate compound may be used alone or in combination of two or more so that the average number of functional groups in the molecule is 3.5 or more.
  • the polyfunctional (meth) acrylate (A) is added to 25 to 100 parts by mass based on a total amount of 100 parts by mass of the polyfunctional (meth) acrylate (A) and the oil-modified alkyd resin (B). It is composed of 45 parts by mass. If it is less than 25 parts by mass, the coating appearance, gloss, heat resistance, water resistance, and moisture resistance are inferior, and if it exceeds 45 parts by mass, the adhesion is lowered, so that the range is limited to the above range. It is preferably 30 to 40 parts by mass.
  • Oil-modified alkyd resin (B) The component (B) of the present invention is an oil-modified alkyd resin.
  • the oil-modified alkyd resin (B) imparts adhesion to FRP.
  • the oil-modified alkyd resin (B) used in the present invention has an oil length of 35 to 50%, an acid value of 0.01 to 10 mgKOH / g, a hydroxyl value of 80 to 130 mgKOH / g, and a weight average molecular weight of 80,000 to 150,000. It is necessary to have.
  • the oil-modified alkyd resin can be obtained by using a fat or oil or a fat or oil fatty acid as a denaturing agent in addition to a polyhydric alcohol and a polybasic acid or an acid anhydride thereof.
  • the polyhydric alcohol used in the oil-modified alkyd resin is not particularly limited, and is, for example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, polyethylene glycol, trimethylene glycol, polypropylene glycol, tetramethylene glycol, poly.
  • Alkylene oxide-modified or lactone-modified polyols polyester polyols having terminal hydroxyl groups obtained by condensing excess of these polyols with polybasic acid or an acid anhydride thereof, polyether polyols, and the like can also be mentioned. can.
  • the polybasic acid or its acid anhydride is not particularly limited, and for example, phthalic acid, isophthalic acid, terephthalic acid, trimetic acid, methylcyclohexcentricarboxylic acid, adipic acid, sebacic acid, azelaic acid, tetrahydrophthalic acid, etc.
  • examples thereof include acids, carbic acids, het acids, aconitic acids, glutaconic acids, and acid anhydrides thereof.
  • the oil or fat fatty acid used as the modifier is not particularly limited and may be any of non-drying oil, semi-drying oil and dry oil, but the iodine value is preferably 80 to 160. There is. Such examples include those selected from the group consisting of tall oil, soybean oil, safflower oil, flax oil, millet oil, castor oil and mixtures of these oils and fats.
  • the iodine value is expressed by the number of grams of iodine that can be added to 100 g of fats and oils, and indicates that the number of double bonds of fatty acids in the sample is large.
  • the iodine value is less than 80, the compatibility with the polyfunctional (meth) acrylate having a double bond is lowered, the appearance is deteriorated, the ultraviolet curability is lowered, and the moisture resistance and the heat resistance are lowered. If it exceeds 160, the amount of the drying oil component increases, so that the storage stability of the alkyd resin and the composition decreases.
  • the oil length of the oil-modified alkyd resin needs to be 35 to 50%.
  • Oil length means a value expressing the oil content based on the weight percentage. If the oil length is less than 35%, the viscosity of the alkyd resin increases, so that the appearance of the coating deteriorates and the mirror surface cannot be finished. Further, when the oil length exceeds 50%, the viscosity of the alkyd resin is lowered, so that liquid dripping occurs after painting and the appearance is deteriorated.
  • the oil-modified alkyd resin (B) used in the present invention needs to have an acid value in the range of 0.01 to 10 mgKOH / g. If the acid value is less than 0.01 mgKOH / g, it takes time to react almost to the end point of the reaction, and the productivity is lowered. If it is larger than 10 mgKOH / g, the storage stability of the oil-modified alkyd resin and the composition is lowered, and the water resistance and moisture resistance of the coating film are lowered.
  • the acid value is preferably 1 to 7 mgKOH / g, more preferably 2 to 5 mgKOH / g.
  • the oil-modified alkyd resin (B) needs to have a weight average molecular weight of 80,000 to 150,000.
  • the weight average molecular weight is measured by gel permeation chromatography (GPC). If the weight average molecular weight is less than 80,000, the film forming property of the coating film is deteriorated and the defects of the FRP material cannot be concealed, so that the appearance is deteriorated and the heat resistance is deteriorated. If it exceeds 150,000, the viscosity becomes high, it is difficult to obtain a smooth coating film flat surface, the appearance is deteriorated, and the mirror surface is not finished after vapor deposition.
  • the weight average molecular weight is preferably 90,000 to 130,000, more preferably 100,000 to 120,000.
  • the undercoat coating composition of the present invention contains the oil-modified alkyd resin (B) in an amount of 55 to 75 parts by mass based on 100 parts by mass of the total amount of the polyfunctional (meth) acrylate (A) and the oil-modified alkyd resin (B). It is composed by containing a portion. If it is less than 55 parts by mass, the adhesion is lowered. If it exceeds 75 parts by mass, the coating appearance, gloss, heat resistance, water resistance, and moisture resistance are inferior.
  • the oil-modified alkyd resin (B) is preferably added in an amount of 60 to 70 parts by mass.
  • Photopolymerization initiator (C) The active energy ray-curable undercoat coating composition of the present invention further contains a photopolymerization initiator (C) to impart active energy ray curability.
  • the photopolymerization initiator (C) is not particularly limited, and for example, benzoin methyl ether, benzoin ethyl ether, benzoin isobutyl ether, benzoin isopropyl ether, benzoin, ⁇ -methylbenzoin, benzoin-n-butyl ether, 2-ethylanthraquinone, etc.
  • 2-t-butylanthraquinone 1-chloranthraquinone, 2-aminoleanthraquinone, 2-aminoanthraquinone, benzophenone, p-chlorbenzophenone, p-dimethylaminobenzophenone, benzophenone methyl ether, methylbenzophenone, 4,4-dichlorobenzophenone, 4,4-Bisdiethylaminobenzophenone, diphenylsulfide, tetramethylthium disulfide, 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, 2,4-diethylthioxanthone, 2-chlorthioxanthone, 2-isopropylthioxanthone, 2, , 2-Dimethoxy-2-phenylacetophenone, ⁇ , ⁇ -dichloro-4-phenyloxyacetone, p-tert-butyl
  • the photopolymerization initiator (C) is applied to a total of 100 parts by mass of the polyfunctional (meth) acrylate (A) and the oil-modified alkyd resin (B). It is composed of 1 to 15 parts by mass. If it is less than 1 part by mass, the active energy ray curing does not proceed, and the adhesion, water resistance, moisture resistance and heat resistance are inferior. If it exceeds 15 parts by mass, an unreacted photopolymerization initiator remains after irradiation with the active energy ray. It has the drawback of becoming a plasticizer and reducing adhesion, water resistance, moisture resistance, heat resistance, and the like. It is preferably 3 to 10 parts by mass.
  • a solvent, a surface conditioner, etc. can be further added in addition to the above components. The solvent has the effect of diluting the undercoat coating composition of the present invention to facilitate coating.
  • the solvent is not particularly limited, and examples thereof include alcohol-based solvents, ketone-based solvents, ester-based solvents, petroleum-based solvents, and the like.
  • Toluene, xylene and the like can be used in combination in order to improve the wettability, but it is preferable not to use them as much as possible in the active energy ray-curable undercoat coating composition of the present invention.
  • the blending amount of the solvent can be increased or decreased as needed, but the amount of xylene used is 3% by weight or less, preferably 1% by weight or less, more preferably with respect to the solid content weight of the undercoat coating composition. It is preferable not to use.
  • the amount of xylene used is 3% by weight or more, environmental regulations become stricter, and high temperature and long-term preheating conditions are required, which is economically disadvantageous.
  • the surface preparation agent is not particularly limited, and examples thereof include a fluorine-based additive and a cellulosic-based additive.
  • the fluorine-based additive has an effect of preventing repelling when applied to an FRP material by lowering the surface tension and increasing the wettability.
  • Specific examples of the fluorine-based additive include Megafuck F-558 (manufactured by Dainippon Ink and Chemicals, Inc.) and the like.
  • the cellulosic additive has an action of imparting film-forming property at the time of application.
  • the undercoat coating composition of the present invention when the amount of the fluorine-based additive is large, the adhesion of steamed aluminum and the top coat is lowered, and when the amount of the cellulose-based additive is large, the undercoat coating composition of the present invention is used. Since the solid content of the above-mentioned is lowered and the coating film is less likely to adhere, it is preferable to use the above-mentioned fluorine additive and the above-mentioned cellulosic additive in combination.
  • the addition amount of the surface preparation agent is the total amount of the fluorine-based additive and the cellulose-based additive with respect to 100% by mass of the solid content of the active energy ray-curable undercoat coating composition of the present invention. , 0.01 to 3.0 parts by mass is preferable. When the above-mentioned fluorine-based additive is used alone, 0.01 to 1.0 part by mass is preferable, and when the above-mentioned cellulose-based additive is used alone, 0.5 to 5.0 parts by mass is preferable. ..
  • the active energy ray-curable coating composition further comprises a surface conditioner, an ultraviolet absorber, a light stabilizer, an antioxidant, a storage stabilizer, an adhesion-imparting agent, an organic or inorganic pigment, an organic bead, as required. It may contain commonly used additives such as inorganic beads and mixtures thereof. These additives can be included in the amount range normally used by those skilled in the art.
  • the surface conditioner is not particularly limited, and is, for example, an acrylic polymer leveling agent, a rust inhibitor, a liquid dripping inhibitor such as amido wax, an electrostatic aid that improves the adhesion of paint, and a vapor-deposited metal.
  • examples include rust preventives.
  • the ultraviolet absorber is not particularly limited, and examples thereof include ultraviolet absorbers such as benzophenone-based, benzotriazole-based, and triazine-based.
  • the light stabilizer is not particularly limited, and examples thereof include a light stabilizer such as a hindered amine type.
  • the antioxidant is not particularly limited, and examples thereof include hindered phenolic antioxidants. Examples of the storage stabilizer include 4-methoxyphenol and dibutylhydroxytoluene.
  • the adhesion-imparting agent is not particularly limited, and examples thereof include a benzotriazole-based adhesion-imparting agent, a silane coupling agent, and a titanium coupling agent.
  • the organic or inorganic pigment is not particularly limited, and examples thereof include silica, alumina, carbon black, and aluminum paste.
  • the organic beads, the inorganic beads and a mixture thereof are not particularly limited, and examples thereof include silica, alumina, acrylic resin beads, urethane resin beads, organic pigments and organic beads containing an inorganic pigment.
  • the undercoat coating composition of the present invention is applied to the surface of the molded product. Then, it is irradiated with ultraviolet rays to form a base coat eyebrows.
  • the above coating can be performed by air spray coating, electrostatic coating, dip coating, or the like.
  • the dry film thickness is set to 8 to 50 ⁇ m, and before the above ultraviolet irradiation, the solvent is evaporated by preheating at 70 to 130 ° C. under the condition of 2 to 25 minutes. If the temperature of the above-mentioned polymer is less than 70 ° C, the solvent remains in the coating film and the water resistance and heat resistance are inferior. There is a drawback that defects and sublimation of the photopolymerization initiator occur, the UV curability is lowered, and the physical properties of the coating film are deteriorated.
  • the evaporation time of the pre-polymer is less than 2 minutes, the solvent remains in the coating film and the water resistance and heat resistance are inferior. If it exceeds 25 minutes, the photopolymerization initiator is sublimated and the ultraviolet curability is lowered. There is a drawback that the physical properties of the coating film are deteriorated.
  • the evaporation time is preferably 2 to 10 minutes, more preferably 2 to 5 minutes, and the solvent is evaporated by preheating.
  • the ultraviolet irradiation can cure the undercoat coating composition of the present invention under the integrated light amount condition of 500 to 5000 mJ / cm2. If the integrated light amount is less than 500 mJ / cm2, there is a drawback that the physical characteristics of the coating film are deteriorated due to insufficient curing by ultraviolet rays. If it exceeds 5000 mJ / cm2, the ultraviolet curability is not affected, but there is a drawback that the material is deformed by the heat from the ultraviolet lamp and the appearance is deteriorated.
  • active energy rays such as high-pressure mercury lamps, metal halide lamps, UV-LED lamps, electron beams, and xenon lamps, which are usually used in the art, can be used for the ultraviolet irradiation.
  • Various layers can be provided on the undercoat layer (sometimes referred to as a "primer layer") formed in this way.
  • the metal vapor deposition layer include an aluminum vapor deposition layer, an indium vapor deposition layer and a tin vapor deposition layer.
  • the metal vapor deposition layer can be provided by a known method such as a vacuum method, a sputtering method (for example, a DC magnetron sputtering method, an RF sputtering method, an ion beam sputtering method, etc.), an electron beam vapor deposition method, an ion plating method, or the like.
  • the metal-deposited layer is an aluminum-deposited layer, it can also be formed by painting a coating composition containing a vapor-deposited aluminum pigment.
  • a coat layer may be provided on the primer layer by using, for example, a known paint composition containing a resin component such as an acrylic resin or a urethane resin. Further, a coat layer may be provided on the metal vapor deposition layer as needed.
  • Polyfunctional (meth) acrylate (A) with 4 or more (meth) aquiloyl groups The following is an example of a polyfunctional (meth) acrylate (A) having four or more (meth) aquiloyl groups in the molecule used in the examples. Most of them are commercial products, and the specific components are described as far as they can be understood. Some of them are synthesized, but the synthesis method will be described as Production Example 1 after the example. When actually used, these polyfunctional (meth) acrylates are used alone or in combination to control the number of reactive groups. The number of functional groups is shown in Tables 3-1 to 4-2.
  • Polyfunctional (meth) acrylate (A) with 4 or more (meth) aquiloyl groups in the molecule The polyfunctional (meth) acrylate (A) having four or more (meth) aquiloyl groups in the molecule is, for example, NK ester A-DPH, NK manufactured by Shin-Nakamura Chemical Co., Ltd. as a mixture of dipentaerythritol hexaacrylate and pentaacrylate.
  • Ester A-9500 Toa Synthetic Aronix M-402, Aronix M-403, Sanyo Kasei Neomer DA600; Aronix M-450 as a mixture of pentaerythritol tetraacrylate and triacrylate; Aronix M-303, Aronix M-305; NK Ester ATMM-3L; Aronix M-408 was used as a mixture of ditrimethylolpropane tetraacrylate and triacrylate.
  • Production Example 1 Production of a trimer of 1,6-hexamethylene diisocyanate and urethane acrylate of hydroxyethyl acrylate In a synthetic container equipped with a cooling tube, a stirrer, a dropping device, and a nitrogen introduction tube, 100 parts of butyl acetate and Asahi Kasei Co., Ltd. 100 parts of Duranate TPA-100 (trifunctional isocyanate) manufactured by Duranate was added.
  • TPA-100 trifunctional isocyanate
  • 2-hydroxyethyl acrylate is added in an amount of 1 equivalent with respect to 1 equivalent of isocyanate groups
  • dibutyltin dilaurylate is added in an amount of 0.1 part
  • dibutylhydroxytoluene is added in an amount of 0.1% with respect to 2-hydroxyethyl acrylate.
  • the mixture was added in an amount, stirred and mixed at room temperature, and then reacted at 80 ° C. for 4 hours under a nitrogen atmosphere to obtain the desired urethane acrylate (number of functional groups: 3).
  • Production Example 2 Production of 1,6-Hexamethylene Diisocyanate and Urethane Acrylate of NK Ester ATMM-3L Duranate TPA-100 (trifunctional isocyanate) manufactured by Asahi Kasei Co., Ltd. in Production Example 1 was changed to 1,6-hexamethylene diisocyanate.
  • the target urethane acrylate (number of functional groups: 6) was obtained by the same method except that 2-hydroxyethyl acrylate was changed to NK ester ATMM-3L.
  • Oil-modified alkyd resin (B) The following describes the production example of the oil-modified alkyd resin used in the examples.
  • the formulations at the time of production are summarized in Tables 1-1, 1-2 and Table 2, and the production methods are described in the following production examples. Some are used in the manufactured examples and some are used in the comparative examples, and the distinction between them is also shown in Tables 1-1 to 2.
  • Tables 1-1 to 2 show the total components during the reaction, the amount of produced water, the iodine value of the obtained oil-modified alkyd resin, the oil length (%), the hydroxyl value, the acid value, and the weight average molecular weight (Mw). , Solid content (%) and xylene amount (%) are also described.
  • Production Example 2 Method for producing an oil-modified alkyd resin containing a large amount of xylene from Patent Document 1 (WO 1995/032250)
  • Alkyd-1 Synthesis of tall oil-modified alkyd resin having an oil length of 39%
  • Tall oil fatty acid 2565 g in a reaction corben. (8.88 mol) and 963 g (6.84 mol) of pentaerythritol were charged, and the temperature was raised to 230 ° C. in 2 hours and 30 minutes while stirring the generated water out of the system.
  • the iodine value of the tall oil fatty acid is 132
  • the hydroxyl value of the obtained alkyd resin is 150 mg / KOH ⁇ g
  • the weight molecular weight is 112,000
  • the solid content is 53.3%
  • the xylene content is 46.7%. there were.
  • Production Example 3 Production method of oil-modified alkyd resin containing almost no xylene Arcido-2: Production of tall oil-modified alkyd resin with an oil length of 39% Tall oil fatty acid 2565 g (8.88 mol) and pentaerythritol 963 g (2.88 mol) in the reaction corben. 6.84 mol) was charged, and the temperature was raised to 230 ° C. in 2 hours and 30 minutes while the generated water was taken out of the system while stirring.
  • Production Example 4 Method for producing an oil-modified alkyd resin containing almost no xylene
  • Alkyd-3 Production of tall oil-modified alkyd resin with a hydroxyl value of 140 mg / KOH ⁇ g and an oil length of 39% Except for changing 506 g (8.16 mol) of ethylene glycol in Production Example 3 to 467.2 g (6.85 mol).
  • a transparent oil-modified alkyd resin solution having an acid value of 4.6 and an oil length of 39% was obtained in the same manner as in Production Example 3.
  • the obtained alkyd resin had a hydroxyl value of 140 mg / KOH ⁇ g, a weight molecular weight of 108,000, a solid content of 53.1%, and a xylene content of 1.2%.
  • Alkyd-6 to 8 were carried out in the same manner as alkyd-5, and a tall oil-modified alkyd resin having a target acid value of 39% and an oil length of 39% was synthesized by adjusting the reaction end point.
  • Alkyd-9 to 12 were carried out in the same manner as in alkyd-5, and a tall oil-modified alkyd resin having a target weight molecular weight and an oil length of 39% was synthesized by adjusting the reaction end point.
  • Alkyd-13 to 17 were carried out in the same manner as Alkyd-5 except that the prescription amounts of tall oil fatty acid and ethylene glycol were adjusted, and a tall oil-modified alkyd resin having a target weight molecular weight and oil length was synthesized.
  • an oil-modified alkyd resin having an oil length of 39% was synthesized by the same method as alkyd-5 except that the tall oil fatty acid was changed to castor oil and safflower oil.
  • Examples 1-42 and Comparative Examples 1-21 The undercoat paints of Examples and Comparative Examples were prepared with the formulations shown in Tables 3-1, 3-2, 4-1 and 4-2, Tables 5 and Table 6.
  • the ingredients are polyfunctional (meth) acrylate (A), oil-modified alkyd resin (B), photoinitiator (benzophenone or 1-hydroxycyclohexylphenylketone) and surface conditioner.
  • Surface modifier Megafuck F-558 and thinner.
  • the formulation also describes the amount of xylene contained in the oil-modified alkyd resin (B).
  • Megafuck F-558 is a surface conditioner commercially available from DIC Corporation.
  • alkyd number means an alkyd-number and means an alkyd resin number.
  • FRP fiber reinforced plastic
  • IPA isopropyl alcohol
  • the undercoat coating composition for each FRP was air-spray coated on the surface thereof so as to have a predetermined dry film thickness as shown in Tables 3-1 to 6. After that, the solvent is removed by preheating under the predetermined conditions shown in Tables 3-1 to 6, and ultraviolet rays are irradiated at an irradiation amount of 3000 mJ / cm 2 using an ozone type diffusion type high-pressure mercury lamp of 80 W / cm 2 .
  • a base coat layer was formed on the surface of the FRP molded product.
  • an overcoat paint is further applied by air spray so as to have a predetermined dry film thickness, and baked under predetermined conditions to obtain a top coat layer.
  • a top coat layer was formed, and an automobile reflector made of FRP was manufactured.
  • the obtained FRP automobile reflector was evaluated by performing a performance test on the following items. The results are shown in Tables 3-1 to 6.
  • Performance test evaluation method 1 Appearance of coating film Visually observe the appearance and inspect for smooth surface condition, rainbow, whitening, cracks, blister, etc., and if there are no defects, ⁇ , rainbow, whitening, crack, blister, etc. Those with slight defects were marked with ⁇ , those with slight defects were marked with ⁇ , and those with defects were marked with ⁇ .
  • the water resistance was immersed in a constant temperature water bath at 40 ° C. for 30 hours, taken out, wiped lightly with a cloth, and the appearance and adhesion were evaluated in the same manner as in the above method.
  • the pot life was stored at 40 ° C for 3 months, the storage stability was observed, and the viscosity did not change significantly. Those without gel generation were evaluated as ⁇ , and those with significant viscosity change or gel generation were evaluated as x.
  • Comparative Examples 1 to 8 use the oil-modified alkyd resin of the example of the old patent (Cited Document 1), and the amount of xylene is high.
  • Comparative Examples 9 to 15 used the alkyd resin-5, and Comparative Examples 9 and 10 showed that the blending amount of the oil-modified alkyd resin (B) deviated from the range of the claims, and Comparative Examples 11 to 11 to 10.
  • Reference numeral 13 is an example in which the number of functional groups of the polyfunctional (meth) acrylate (A) is insufficient.
  • Comparative Examples 14 to 21 the hydroxyl value, acid value, etc. of the oil-modified alkyd resin (B) are out of the range of claim 1.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Paints Or Removers (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

L'invention a pour objet de fournir une composition qui ne met en œuvre presque pas de xylène en tant que solvant, qui améliore les propriétés de séchage et la résistance à l'humidité, et qui peut être mise en œuvre en tant que revêtement de peinture primaire pour élément réfléchissant d'éclairage automobile compatible avec une ampoule à DEL.　Plus précisément, l'invention fournit une composition de revêtement de peinture primaire durcissable par rayonnement actinique pour plastique renforcé de fibres qui effectue une déposition métallique contenant un (méth)acrylate fonctionnel (A) et une résine alkyde (B) modifiée par une huile. Ledit (méth)acrylate fonctionnel (A) possède au moins quatre groupes (méth)acryloyle à l'intérieur de chaque molécule, et est compris selon une quantité de 25 à 45 parties en masse pour 100 parties en masse de quantité totale dudit (méth)acrylate fonctionnel (A) et de ladite résine alkyde (B) modifiée par une huile. Ladite résine alkyde (B) modifiée par une huile est comprise selon une quantité de 55 à 75 parties en masse pour 100 parties en masse de quantité totale dudit (méth)acrylate fonctionnel (A) et de ladite résine alkyde (B) modifiée par une huile. Enfin, ladite résine alkyde (B) modifiée par une huile présente un rapport huile/résine compris entre ３５ et ５０％, un indice d'acide compris entre ０,０１ et １０ｍｇＫＯＨ／ｇ, un indice d'hydroxyle compris entre ８０ et １３０ｍｇＫＯＨ／ｇ, et une masse moléculaire moyenne en poids comprise entre ８００００ et １５００００.
PCT/JP2021/048273 2020-12-28 2021-12-24 Composition de revêtement de peinture primaire durcissable par rayonnement actinique pour plastique renforcé de fibres WO2022145376A1 (fr)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003221408A (ja) * 2002-01-30 2003-08-05 Nippon Synthetic Chem Ind Co Ltd:The 紫外線硬化型樹脂組成物、塗膜形成方法及びその用途
WO2015019898A1 (fr) * 2013-08-07 2015-02-12 Dic株式会社 Composition de résine durcissable par rayons énergétiques actifs, agent de couche intermédiaire la contenant, et article moulé
JP2016199690A (ja) * 2015-04-10 2016-12-01 関西ペイント株式会社 塗料組成物
JP2017039792A (ja) * 2015-08-17 2017-02-23 Dic株式会社 活性エネルギー線硬化型樹脂組成物、これを含有する下塗り用コーティング剤及び成形体
JP2017039791A (ja) * 2015-08-17 2017-02-23 Dic株式会社 活性エネルギー線硬化型樹脂組成物、これを含有する下塗り用コーティング剤及び成形体
WO2018012295A1 (fr) * 2016-07-14 2018-01-18 Dic株式会社 Composition de résine durcissable par rayonnement d'énergie active et agent de sous-couche à film mince métallique
JP2018177844A (ja) * 2017-04-04 2018-11-15 関西ペイント株式会社 塗料組成物及び複層塗膜形成方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003221408A (ja) * 2002-01-30 2003-08-05 Nippon Synthetic Chem Ind Co Ltd:The 紫外線硬化型樹脂組成物、塗膜形成方法及びその用途
WO2015019898A1 (fr) * 2013-08-07 2015-02-12 Dic株式会社 Composition de résine durcissable par rayons énergétiques actifs, agent de couche intermédiaire la contenant, et article moulé
JP2016199690A (ja) * 2015-04-10 2016-12-01 関西ペイント株式会社 塗料組成物
JP2017039792A (ja) * 2015-08-17 2017-02-23 Dic株式会社 活性エネルギー線硬化型樹脂組成物、これを含有する下塗り用コーティング剤及び成形体
JP2017039791A (ja) * 2015-08-17 2017-02-23 Dic株式会社 活性エネルギー線硬化型樹脂組成物、これを含有する下塗り用コーティング剤及び成形体
WO2018012295A1 (fr) * 2016-07-14 2018-01-18 Dic株式会社 Composition de résine durcissable par rayonnement d'énergie active et agent de sous-couche à film mince métallique
JP2018177844A (ja) * 2017-04-04 2018-11-15 関西ペイント株式会社 塗料組成物及び複層塗膜形成方法

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