WO2006046117A1 - White basecoat coating composition, method for forming coating film and coated article - Google Patents

White basecoat coating composition, method for forming coating film and coated article Download PDF

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Publication number
WO2006046117A1
WO2006046117A1 PCT/IB2005/003186 IB2005003186W WO2006046117A1 WO 2006046117 A1 WO2006046117 A1 WO 2006046117A1 IB 2005003186 W IB2005003186 W IB 2005003186W WO 2006046117 A1 WO2006046117 A1 WO 2006046117A1
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WIPO (PCT)
Prior art keywords
coating material
base coating
coated
white base
wet
Prior art date
Application number
PCT/IB2005/003186
Other languages
French (fr)
Inventor
Masato Tokieda
Kazunori Kawahara
Masao Nakata
Original Assignee
Basf Coatings Japan Ltd.
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Filing date
Publication date
Application filed by Basf Coatings Japan Ltd. filed Critical Basf Coatings Japan Ltd.
Publication of WO2006046117A1 publication Critical patent/WO2006046117A1/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/56—Three layers or more
    • B05D7/57—Three layers or more the last layer being a clear coat
    • B05D7/572—Three layers or more the last layer being a clear coat all layers being cured or baked together
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/02—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber
    • 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
    • C09D7/48—Stabilisers against degradation by oxygen, light or heat
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2201/00—Polymeric substrate or laminate
    • B05D2201/02—Polymeric substrate
    • 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
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2

Definitions

  • the present invention relates to white base coating material compositions, wherein yellowing of coated films over time, due to sunlight (or heat) , is pre- vented by a system wherein: a white base coat material is applied onto a coated film of a conductive primer, formed by coating the primer onto a polyolefin substrate and drying; a mica base coating material is coated by means of a wet on wet technique onto the white base coating material; and a clear coating material is coated onto this mica base coating material by means of a wet on wet technique.
  • the present invention relates to a process for forming coated films wherein these white base coating material compositions are used and to products wherein coating has been carried out by means of this process.
  • phenol-based antioxidants are widely known among antioxidants; and hydroxylamine is an organic substance which is known to be particularly effective for the protection of polyolefins containing phenol- based antioxidants from yellowing (c.f., for example, Patent Reference 3) .
  • Non-yellowing primer compositions for automobiles are also known wherein there is joint use of primers con ⁇ taining polyolefin-based resins or chlorinated polyole- fin-based resins and epoxy resins as primer compo- sitions for the polyolefin materials and of phosphorus- based antioxidants and hindered phenol-based antioxi ⁇ dants, (c.f., for example, Patent Reference 4) .
  • the primer materials are added to phenol-based antioxidants which bleed from the materials; and acidic products of phenol-based anti ⁇ oxidants (quinone compounds) are also produced, because of the compounding in of the phenol-based antioxidants, so that there is the drawback of marked yellowing of coated films with the passage of time, due to these substances.
  • Coating compositions are also known wherein the stabilities of the main volatile components are ascertained from within a polyolefin substrate; a metal deactivator is used as an indispensable component, by specifying the volatile components which are the cause of yellowing; and a phosphite-based antioxidant and/or a dechlorination catcher are added as required (c.f., for example, Patent Reference 5) .
  • a metal deactivator is used as an indispensable component, by specifying the volatile components which are the cause of yellowing
  • a phosphite-based antioxidant and/or a dechlorination catcher are added as required (c.f., for example, Patent Reference 5) .
  • the present invention is to provide : white base coating material compositions , whereby it is possible to form, on polyolef in substrates , coated f ilms of l ight colors wherein clear colors endure, without yellowing with the passage of time due to sunlight (or heat) ; a process for the formation of coated films using these compositions; and coated products.
  • the present invention provides white base coating material compositions, characterized in that they are the white base coating materials containing titanium oxide in a process wherein these white base coating materials are applied onto a coated film formed by coating a film of a conductive primer onto a polyolefin substrate and drying; a light-colored mica base coating material is coated onto the white base coating material by a wet on wet technique; and a clear coating material is coated onto the mica base coating material by a wet on wet technique, after which a coated film is formed by thermal hardening in a three- coat one-bake procedure; the compositions contain 0.2 to 5.0 parts by mass of a biphenyl phosphate compound represented by formula (1) per 100 parts by mass of the solid resin fraction.
  • R 1 and R 2 each independently represent a hydrogen atom, halogen atom, a hydrocarbon of 1 to 6 carbon atoms or a halogenated hydrocarbon of 1 to 6 carbon atoms; and m and n represent integers from 0 to 4.
  • the invention also provides white base coating material compositions wherein R 1 and R 2 in the biphenyl phosphate represented by formula (1) are both hydrogen atoms.
  • the invention further provides a process for the formation of coated films, wherein: a white base coating material, as claimed in claim 1 or 2, is applied onto a coated film, formed by coating a conductive primer onto a polyolefin substrate and drying; a mica base coating material is coated onto the white base coating material by a wet on wet technique; and a clear coating material is coated onto this mica base coating material by means of a wet on wet technique, after which a coated film is formed by thermal hardening in a three-coat one-bake procedure.
  • a white base coating material as claimed in claim 1 or 2
  • a mica base coating material is coated onto the white base coating material by a wet on wet technique
  • a clear coating material is coated onto this mica base coating material by means of a wet on wet technique, after which a coated film is formed by thermal hardening in a three-coat one-bake procedure.
  • the invention yet further provides coated products wherein coating has been carried out by means of the above-mentioned coating formation process.
  • the white base compositions according to the present invention it is possible to obtain light colors which are stable to sunlight (or heat) and wherein yellowing with the passage of time can be prevented, even in cases where the substrates are polyolefins.
  • polypropylene resins examples which may be given of the components which constitute the polyolefins according to the present invention are polypropylene resins and polypropylene resin-based alloys.
  • Polypropylene resin-based alloys are composite materials wherein a polypropylene resin and 1 or more other types of polymers are physically mixed; they are known as materials which have an overall synergistic utility and performance.
  • polypropylene resin-based alloys are not particu ⁇ larly restricted, but examples of polymer alloys which may be given comprise 5% to 95% by mass of a polypropylene resin and 95% to 5% of other resins. Examples which may be given of polypropylene resin- based alloys wherein the effects of the present invention are more readily exhibited are those with polypropylene resin, 50 to 95% by mass, more preferably 60 to 95% by mass and other resins for alloying, 50 to 5% by mass, more preferably 40 to 5% by mass.
  • Representative examples which may be given of the other resins for alloys are: polyamide resins, polyethylene terephthalate resins, polybutylene terephthalate resins, polyvinyl chloride resins, ethylene-propylene- diene monomer copolymer rubbers (EPDM) , ethylene-pro- pylene copolymer rubbers (EPR) and thermoplastic elast ⁇ omers.
  • the other resins for alloys may be used singly or as combinations of 2 or more of them.
  • these other resins for alloys may be partially modified, in order to enable miscibility and dispersion to be designed in and they may be used in conjunction with agents to facilitate miscibility.
  • the polyolefin substrates contain plasticizers, the characteristics of the present invention are fully displayed.
  • the polyolefin substrates may contain 1, 2 or more of, for example: ultraviolet absorbents, antioxidants, release agents, antistatic agents, colorants, flame retardants, fiber reinforcing agents, such as glass fibers, and inorganic fillers.
  • Examples of the forms of the polyolefin substrates which may be given are various forms, such as: films, sheet, plate and three-dimensional forms.
  • the conductive primers used according to the present invention denote primers wherein conductive materials are contained.
  • the primers are coating materials which are directly coated onto polyolefin substrates and they perform the role of adhesion to the substrates.
  • the primers have good adhesion to both the polyolefin resin substrates and the base coats and final coats and it is best if materials are selected which have flexibilities corresponding to the flexibilities of the substrates; primers are used wherein polypropylene resins and chlorinated polypropylene resins are employed.
  • Examples of the conductive materials which may be used in the conductive primers are white conductive materials, such as titanium dioxide, whereon are coated metal powders, such as nickel or copper, carbon or tin oxide.
  • the conductive materials in the conductive primer layer are mutually in contact, so that conductivity is imparted to the whole coated film surface.
  • the content of a conductive material is selected from within a range wherein appropriate conductivity is shown, but it is normally preferable to have 0.1 to 40 parts by mass per 100 parts by mass of the solid fraction of the conductive primer.
  • the process for coating a conductive primer is not particularly restricted according to the present invention, for example, coating may be by means of air spray application, airless spray application and low pressure atomization spray application (high volume low pressure, HVLP) .
  • the thickness of the coated film is not particularly restricted, but it is preferable, in order to exhibit the conductivity of the coated film, to have a hardened coated film thickness of 5 to 15 ⁇ m.
  • the white base coating material compositions used according to the present invention are coating materials which form white-based coated films: their main components are resin components, titanium dioxide pigment and solvents. When required, colored pigments, fillers and additives for coating materials may be used.
  • the resin components of the white base coating material compositions are preferably thermosetting resin compositions; and it is particularly preferable for the base resin to be made an acrylic resin, polyester resin, alkyd resin, urethane resin, or the like, having cross-linkable functional groups, such as hydroxyl groups and combined with a resin for cross-linking, such as melamine resins and block polyisocyanate compounds .
  • the colors of the white base coating material compo- sitions preferably have L values of coated films of 80 or more, when determined by means of a colorimeter, so that, for this reason, it is preferable to have a content of titanium dioxide pigment of 30 to 150 parts by mass, particularly preferably 50 to 90 parts by mass, to 100 parts by mass of the resin solid fraction.
  • the titanium dioxide pigment content is less than 30 parts by mass, it is impossible to obtain a white coated film which has an L value of 80 or more, because the covering power is inadequate; and, when the titanium dioxide content exceeds 150 parts by mass, the flexibility of the coated film and the adhesion to the substrate are poor.
  • R 1 and R 2 each independently represent a hydrogen atom, halogen atom, a hydrocarbon of 1 to 6 carbon atoms, or a halogenated hydrocarbon of 1 to 6 carbon atoms; and m and n represent integers from 0 to 4.
  • halogen atoms in formula (1) examples are: fluorine atoms, chlorine atoms, bromine atoms and iodine atoms.
  • m and n in formula (1) are preferably integers from 0 to 2, particularly preferably integers from 0 to 1.
  • biphenyl phosphate compounds represented by formula (1) are readily obtained by heating and condensing, in the presence of a Friedel-Crafts type catalyst, such as aluminum chloride or zinc chloride, an ortho-phenylphenol (or a nuclear substituted derivative thereof) , such as ortho- phenylphenol (2-hydroxyphenol) , 2-hydroxy-3, 5, 4' -tri- chlorobiphenyl, 2-hydroxy-3, 5, 4' -tribromobiphenyl, 2- hydroxy-3, 5-dichloro-4' -nitrobiphenyl, 2-hydroxy-5-oct- ylbiphenyl, 2-hydroxy-3-acetylbiphenyl, 4-hydroxy-phen- anthrene and 2-hydroxy-5,4' -dimethylbiphenyl, and phos ⁇ phorus trichloride, phosphorus tribromide, or the like.
  • a Friedel-Crafts type catalyst such as aluminum chloride or zinc chloride
  • an ortho-phenylphenol
  • R 1 and R 2 in formula (1) which may be given are: chlorine atoms, bromine atoms, methyl, ethyl, isopropyl, butyl, pentyl, neopentyl, hexyl, chloromethyl, bromomethyl, dichloromethyl and trichloromethyl .
  • the content of a biphenyl phosphate compound repre ⁇ sented by formula (1) which is used according to the present invention, is preferably 0.2 to 5.0 parts by mass per 100 parts by mass of the resin solid fraction of a white base coat. There is particularly preferably 0.8 to 4.5 parts by mass.
  • biphenyl phosphate compound content is less than 0.2 parts by mass, the effect to control yellowing of coated films is inadequate; and, when it exceeds 5.0 parts by mass, the water resistance and moisture resistance of coated films are poor.
  • additives which may be used for coating materials are: ultraviolet absorbents, such as benzo- triazole and oxanilide-based compounds, antioxidants, such as benzophenol-based compounds, leveling agents, such as silicone-based compounds, waxes, viscosity regulators, such as organobentonites and curing catalysts.
  • ultraviolet absorbents such as benzo- triazole and oxanilide-based compounds
  • antioxidants such as benzophenol-based compounds
  • leveling agents such as silicone-based compounds, waxes
  • viscosity regulators such as organobentonites and curing catalysts.
  • Solvents may be compounded into the white base coating material compositions, as required. Examples which may be given of the solvents are aliphatic hydrocarbon- based solvents and aromatic hydrocarbon-based solvents. The solvent content is selected so that it is within a suitable range whereby the viscosity of the coating material is such that it may be coated.
  • coating may be by air spray application, airless spray application or electrostatic application, but it is preferable to use electrostatic application when coating onto the surface of a conductive primer.
  • coated films of white base coating materials there is no particular restriction on the thickness of coated films of white base coating materials according to the present invention, but, in order to cover the primers and obtain the desired L values, it is preferable to have a hardened coated film thickness of 5 to 50 ⁇ m, particularly preferably 6 to 25 ⁇ m.
  • the resin components of the light-colored mica base coating material compositions which are used according to the present invention are preferably thermosetting resin compositions similar to the white base coating material compositions and it is particularly preferable to have combinations of base resins having cross- linkable functional groups such as hydroxyl groups, for example: acrylic resins, polyester resins, alkyd resins and urethane resins and of resins for cross-linking, such as melamine resins and block polyisocyanate compounds .
  • the mica pigments used according to the present invention have white pearl pigments and/or silver pearl pigments as indispensable components and colored mica pigments, colored pigments, extender pigments and dyes may be used as required.
  • the pigments termed "white pearl pigments” and “silver pearl” pigments are in the form of flake mica powder coated with titanium dioxide.
  • the quantities to compound of titanium dioxide-coated flake mica powder in mica base coating materials are preferably 3 to 20 parts by mass, particularly preferably 5 to 12 parts by mass, per 100 parts by mass of solid resin fraction.
  • the resin components of the clear coating materials used according to the present invention are preferably thermosetting resin compositions, similar to the white base compositions and it is particularly preferable to have combinations of base resins having cross-linkable functional groups such as hydroxyl groups, for example: acrylic resins, polyester resins, alkyd resins and urethane resins and of resins for cross-linking, such as melamine resins and block polyisocyanate compounds.
  • base resins having cross-linkable functional groups such as hydroxyl groups
  • acrylic resins acrylic resins, polyester resins, alkyd resins and urethane resins
  • resins for cross-linking such as melamine resins and block polyisocyanate compounds.
  • Solvents may also be compounded into the conductive primers, mica base coating material compositions and clear coating materials, as required.
  • the solvents which may be given are organic solvents, such as aromatic hydrocarbon solvents, for instance, toluene and xylene; ketone solvents, for instance, acetone and methyl ethyl ketone; ester solvents, for instance, ethyl acetate and butyl cellosolve,- and alcohol solvents, or mixtures thereof.
  • the solvent content is selected so that it is in a suitable range for the viscosity of the coating material to enable coating.
  • the process for the formation of several coated films used according to the invention can further promote the design properties, finished appearance, weather resistance, chemical resistance, water resistance, moisture resistance, and the like, of the coated films, by the application of a conductive primer to a polyolefin substrate and drying, after which a white base coating material composition, mica base coating material composition, clear coating material are applied in turn by means of a wet on wet technique and baked.
  • the coating process for the clear coating material there is no particular restriction on the coating process for the clear coating material, but it is preferable to use electrostatic coating, in a similar manner to that for the white base coating material and the mica base coating material.
  • the thickness of coated films of clear coating materials there is no particular restriction on the thickness of coated films of clear coating materials, but the hardened coated film thick ⁇ ness is preferably 15 to 50 ⁇ m.
  • hardening temperature 70° to 150 0 C.
  • suitable times are 10 to 60 minutes at a hardening temperature of 70° to 15O 0 C.
  • White Base coating material compositions 2 to 9 were manufactured in a similar manner to White Base coating material composition 1, with the exceptions to the proportions of the mixtures listed in Table 1 and Table 2. [0033] [Table 1]
  • Biphenyl phosphate compound HCA (manufactured by Sanko Kagaku (K K) (Sanko Chemical Company Limited); 9, 10-dihydro-9-oxa-10-phosphaphenan- threne-10-oxide)
  • Phosphorus-based antioxidant Adekastab [manufactured by Asahi Denka Kogyo K K; tris(2,4-di-tertiary-butylphenyl)phosphate]
  • Hindered phenol Sumilizer GA-80 [manufactured by Sumitomo Kagaku (K K) (Sumitomo Chemical Company Limited); 3, 9-bis ⁇ l,l-dimethyl-2- [ ⁇ - (3- tertiary-butyl-4-hydroxy-5-methylphenyl)propionyloxy] 2,4,8,10-tetraoxa- spiro[5,5] -undecane ⁇
  • a mixture was made of: an acrylic resin (100 parts by mass; manufactured by BASF Coatings Japan Limited; Trade Name "LB-9020"; heating residue, 55% by mass; hydroxyl value, 56 mg KOH/g) ; an amino resin [20 parts by mass; manufactured by Mitsui Kagaku (K.
  • Dirt and dust were removed from a commercial black polypropylene sheet (length, 70 mm; width, 150 mm; thickness, 3 mm) by wiping the surface of this material to be coated with isopropyl alcohol .
  • a chlorinated polypropylene resin-based conductive primer (manufac ⁇ tured by BASF Coatings Japan Limited; Trade Name Puraimakku 1501) ; conductive material, conductive carbon, content of conductive material, 1 to 5 parts by mass; MSDS display) , which had its viscosity adjusted so that it was 11 seconds, under the conditions, a Ford Cup with a Number 4 orifice, at 20 0 C, was applied, in xylene, with an air spray, so that the dried coated film thickness was 6 to 8 ⁇ m.
  • the material was kept at room temperature for 2 minutes, after which White Base Coating Material Composition 1, which had had its viscosity adjusted so that it was 15 seconds, under the conditions, a Ford Cup with a Number 4 orifice, at 2O 0 C, was electrostatically applied, such that the dried coated film thickness was 15 ⁇ m.
  • the viscosity of a mica base coating material (amount compounded of titanium dioxide coated flake mica powder, 5.5 parts by mass to 100 parts by mass of solid resin component) was adjusted so that it was 15 seconds, under the conditions, a Ford Cup with a Number 4 orifice, at
  • Example 2 These were carried out in a similar manner to that for Example 1, changing just the white base coats to those listed in Table 1 and Table 2; test plates were prepared and tests were carried out.
  • Test boards were kept at for 90 days in a dryer set at a temperature of 8O 0 C, taken out and their b values determined after 1 hour with a CR-200 colorimeter [manufactured by Minolta (K K) ] .
  • K K Minolta
  • ⁇ b (b value after thermal resistance test) - (b value before thermal resistance test)
  • a thermostatic water bath (set temperature 35°C) fitted with a stirrer was filled with deionized water and test plates were immersed in it for 240 hours. Water was removed from the test plates with paper towels, the plates were kept at room temperature for 1 hour, after which the adhesive properties of the coated films were appraised. The results of the appraisals were the same for the adhesive properties of the above-mentioned coated films.

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  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
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Abstract

To provide white base coating material compositions which can form light-colored coated films on polyolefin substrates, whereby fresh colors are maintained, without yellowing with the passage of time, due to sunlight (or heat). [The Means of Solution] A white base coating material containing titanium dioxide, which is the white base coating material in a process wherein it is applied onto a film of a conductive primer which has been coated onto a polyolefin substrate and dried; a light­colored mica base coating material is applied onto the white base coating material by a wet on wet technique; and a clear coating material is applied onto this mica base coating material, after which a coated film is formed by thermal hardening by a three-coat one-bake procedure; the white base coating material compositions contain 0.2 to 5.0 parts by mass of a biphenyl phosphate compound represented by formula (1) per 100 parts by mass of a resin solid fraction; a process for the formation of coated films using these white base coating material compositions; and coated products therefrom.

Description

White basecoat coating composition, method for forming coating film and coated article
[1. Field of the Invention] [0001]
The present invention relates to white base coating material compositions, wherein yellowing of coated films over time, due to sunlight (or heat) , is pre- vented by a system wherein: a white base coat material is applied onto a coated film of a conductive primer, formed by coating the primer onto a polyolefin substrate and drying; a mica base coating material is coated by means of a wet on wet technique onto the white base coating material; and a clear coating material is coated onto this mica base coating material by means of a wet on wet technique. In further detail, the present invention relates to a process for forming coated films wherein these white base coating material compositions are used and to products wherein coating has been carried out by means of this process.
[Background Art] [0002] At present, clear, light paint colors are obtained in coated products wherein polyolefins are used as sub¬ strates for automobile bumpers and the like. In general, the object of producing coated films may be achieved, for the exterior parts of automobiles, by processes wherein several white-based coated films are formed by applying electrodeposition coating materials, intermediate coating materials, white base coating materials, white pearl coating materials or silver pearl coating materials and clear coating materials (c.f. for example, Patent References 1 and 2) . [0003]
It is considered that, when this process is applied to polyolefin substrates, electrodeposition coating is unnecessary: a conductive primer is used instead of an intermediate coat, then a white base coat material, white pearl coating material or silver pearl base coating material and a clear coating material are applied, but polyolefin substrates differ from the case of metallic materials such as automobile exterior panels and there is the drawback that coated films yellow with the passage of time. It is considered that this is due to the bleeding of materials which are contained within the plasticizers of the polyolefin substrates and this phenomenon is particularly accelerated when heat is applied.
[0004]
In general, phenol-based antioxidants are widely known among antioxidants; and hydroxylamine is an organic substance which is known to be particularly effective for the protection of polyolefins containing phenol- based antioxidants from yellowing (c.f., for example, Patent Reference 3) .
However, in the case of light-colored coated films, wherein polyolefins are used as substrates, this effect is inadequate and there is the drawback of yellowing with the passage of time, due to sunlight (or heat) .
[0005]
Non-yellowing primer compositions for automobiles are also known wherein there is joint use of primers con¬ taining polyolefin-based resins or chlorinated polyole- fin-based resins and epoxy resins as primer compo- sitions for the polyolefin materials and of phosphorus- based antioxidants and hindered phenol-based antioxi¬ dants, (c.f., for example, Patent Reference 4) . How- ever, in this process, the primer materials are added to phenol-based antioxidants which bleed from the materials; and acidic products of phenol-based anti¬ oxidants (quinone compounds) are also produced, because of the compounding in of the phenol-based antioxidants, so that there is the drawback of marked yellowing of coated films with the passage of time, due to these substances.
[0006]
Coating compositions are also known wherein the stabilities of the main volatile components are ascertained from within a polyolefin substrate; a metal deactivator is used as an indispensable component, by specifying the volatile components which are the cause of yellowing; and a phosphite-based antioxidant and/or a dechlorination catcher are added as required (c.f., for example, Patent Reference 5) . However, there are the drawbacks with this process that there are cases wherein there is deactivation of metal ions, due to the formation of metal complexes from a metal deactivator, and the product complex is colored; and that there are cases wherein yellowing, which occurs with the passage of time after coating film formation, is promoted.
[007]
[Patent Reference 1] Japanese Ciiexamiπed Patent Application 8-164358
Japanese Utiexamined Patent Application 2002-205006 Japanese Examined Patent Application 7-25726 Japanese IMexaπύned Patent Application 7-118568
Japanese liiexaπάned Patent Application 10-28924 [DISCLOSURE OF THE INVENTION] [Problems to be Solved by the Invention] [ 0008 ] The present invention is to provide : white base coating material compositions , whereby it is possible to form, on polyolef in substrates , coated f ilms of l ight colors wherein clear colors endure, without yellowing with the passage of time due to sunlight (or heat) ; a process for the formation of coated films using these compositions; and coated products.
[The Means of Solving the Problems] [0009]
That is, the present invention provides white base coating material compositions, characterized in that they are the white base coating materials containing titanium oxide in a process wherein these white base coating materials are applied onto a coated film formed by coating a film of a conductive primer onto a polyolefin substrate and drying; a light-colored mica base coating material is coated onto the white base coating material by a wet on wet technique; and a clear coating material is coated onto the mica base coating material by a wet on wet technique, after which a coated film is formed by thermal hardening in a three- coat one-bake procedure; the compositions contain 0.2 to 5.0 parts by mass of a biphenyl phosphate compound represented by formula (1) per 100 parts by mass of the solid resin fraction.
[0010]
[Chemical Expression 2 ]
Figure imgf000005_0001
[ 0011 ] (in which formula: R1 and R2 each independently represent a hydrogen atom, halogen atom, a hydrocarbon of 1 to 6 carbon atoms or a halogenated hydrocarbon of 1 to 6 carbon atoms; and m and n represent integers from 0 to 4. )
The invention also provides white base coating material compositions wherein R1 and R2 in the biphenyl phosphate represented by formula (1) are both hydrogen atoms.
The invention further provides a process for the formation of coated films, wherein: a white base coating material, as claimed in claim 1 or 2, is applied onto a coated film, formed by coating a conductive primer onto a polyolefin substrate and drying; a mica base coating material is coated onto the white base coating material by a wet on wet technique; and a clear coating material is coated onto this mica base coating material by means of a wet on wet technique, after which a coated film is formed by thermal hardening in a three-coat one-bake procedure.
The invention yet further provides coated products wherein coating has been carried out by means of the above-mentioned coating formation process.
[Operation of the Invention]
[0012]
By using the white base compositions according to the present invention, it is possible to obtain light colors which are stable to sunlight (or heat) and wherein yellowing with the passage of time can be prevented, even in cases where the substrates are polyolefins.
[Best Mode of Carrying out the Invention]
[0013] The present invention will be described in detail hereunder.
Examples which may be given of the components which constitute the polyolefins according to the present invention are polypropylene resins and polypropylene resin-based alloys. Polypropylene resin-based alloys are composite materials wherein a polypropylene resin and 1 or more other types of polymers are physically mixed; they are known as materials which have an overall synergistic utility and performance.
The polypropylene resin-based alloys are not particu¬ larly restricted, but examples of polymer alloys which may be given comprise 5% to 95% by mass of a polypropylene resin and 95% to 5% of other resins. Examples which may be given of polypropylene resin- based alloys wherein the effects of the present invention are more readily exhibited are those with polypropylene resin, 50 to 95% by mass, more preferably 60 to 95% by mass and other resins for alloying, 50 to 5% by mass, more preferably 40 to 5% by mass.
[0014] Representative examples which may be given of the other resins for alloys are: polyamide resins, polyethylene terephthalate resins, polybutylene terephthalate resins, polyvinyl chloride resins, ethylene-propylene- diene monomer copolymer rubbers (EPDM) , ethylene-pro- pylene copolymer rubbers (EPR) and thermoplastic elast¬ omers. The other resins for alloys may be used singly or as combinations of 2 or more of them.
In addition, these other resins for alloys may be partially modified, in order to enable miscibility and dispersion to be designed in and they may be used in conjunction with agents to facilitate miscibility. [0015]
When the polyolefin substrates contain plasticizers, the characteristics of the present invention are fully displayed. In addition, in order for the polyolefin substrates to have satisfactory characteristics which accord with usage, they may contain 1, 2 or more of, for example: ultraviolet absorbents, antioxidants, release agents, antistatic agents, colorants, flame retardants, fiber reinforcing agents, such as glass fibers, and inorganic fillers.
Examples of the forms of the polyolefin substrates which may be given are various forms, such as: films, sheet, plate and three-dimensional forms.
[0016]
The conductive primers used according to the present invention denote primers wherein conductive materials are contained. The primers are coating materials which are directly coated onto polyolefin substrates and they perform the role of adhesion to the substrates. The primers have good adhesion to both the polyolefin resin substrates and the base coats and final coats and it is best if materials are selected which have flexibilities corresponding to the flexibilities of the substrates; primers are used wherein polypropylene resins and chlorinated polypropylene resins are employed.
[0017]
Examples of the conductive materials which may be used in the conductive primers are white conductive materials, such as titanium dioxide, whereon are coated metal powders, such as nickel or copper, carbon or tin oxide. The conductive materials in the conductive primer layer are mutually in contact, so that conductivity is imparted to the whole coated film surface.
The content of a conductive material is selected from within a range wherein appropriate conductivity is shown, but it is normally preferable to have 0.1 to 40 parts by mass per 100 parts by mass of the solid fraction of the conductive primer.
[0018]
The process for coating a conductive primer is not particularly restricted according to the present invention, for example, coating may be by means of air spray application, airless spray application and low pressure atomization spray application (high volume low pressure, HVLP) . The thickness of the coated film is not particularly restricted, but it is preferable, in order to exhibit the conductivity of the coated film, to have a hardened coated film thickness of 5 to 15 μm.
The white base coating material compositions used according to the present invention are coating materials which form white-based coated films: their main components are resin components, titanium dioxide pigment and solvents. When required, colored pigments, fillers and additives for coating materials may be used.
[0019] The resin components of the white base coating material compositions are preferably thermosetting resin compositions; and it is particularly preferable for the base resin to be made an acrylic resin, polyester resin, alkyd resin, urethane resin, or the like, having cross-linkable functional groups, such as hydroxyl groups and combined with a resin for cross-linking, such as melamine resins and block polyisocyanate compounds .
The colors of the white base coating material compo- sitions preferably have L values of coated films of 80 or more, when determined by means of a colorimeter, so that, for this reason, it is preferable to have a content of titanium dioxide pigment of 30 to 150 parts by mass, particularly preferably 50 to 90 parts by mass, to 100 parts by mass of the resin solid fraction.
[0020]
When the titanium dioxide pigment content is less than 30 parts by mass, it is impossible to obtain a white coated film which has an L value of 80 or more, because the covering power is inadequate; and, when the titanium dioxide content exceeds 150 parts by mass, the flexibility of the coated film and the adhesion to the substrate are poor.
A process for the manufacture of biphenyl phosphates represented by formula (1) , which are used according to the present invention is published in Japanese Unexamined Patent Application 2004-35495. 9, 10-Dihydro- 9-oxa-lO-phosphaphenanthrene-lO-oxide, wherein R1 and R2 are both hydrogen atoms, is commercially available.
[0021]
[Chemical Expression 3]
Figure imgf000010_0001
(in which formula: R1 and R2 each independently represent a hydrogen atom, halogen atom, a hydrocarbon of 1 to 6 carbon atoms, or a halogenated hydrocarbon of 1 to 6 carbon atoms; and m and n represent integers from 0 to 4. )
Examples which may be given of the halogen atoms in formula (1) are: fluorine atoms, chlorine atoms, bromine atoms and iodine atoms.
[0023] m and n in formula (1) are preferably integers from 0 to 2, particularly preferably integers from 0 to 1.
The biphenyl phosphate compounds represented by formula (1) , as published in Japanese Examined Patent Application 49-45397, are readily obtained by heating and condensing, in the presence of a Friedel-Crafts type catalyst, such as aluminum chloride or zinc chloride, an ortho-phenylphenol (or a nuclear substituted derivative thereof) , such as ortho- phenylphenol (2-hydroxyphenol) , 2-hydroxy-3, 5, 4' -tri- chlorobiphenyl, 2-hydroxy-3, 5, 4' -tribromobiphenyl, 2- hydroxy-3, 5-dichloro-4' -nitrobiphenyl, 2-hydroxy-5-oct- ylbiphenyl, 2-hydroxy-3-acetylbiphenyl, 4-hydroxy-phen- anthrene and 2-hydroxy-5,4' -dimethylbiphenyl, and phos¬ phorus trichloride, phosphorus tribromide, or the like. Suitable specific embodiment examples of R1 and R2 in formula (1) which may be given are: chlorine atoms, bromine atoms, methyl, ethyl, isopropyl, butyl, pentyl, neopentyl, hexyl, chloromethyl, bromomethyl, dichloromethyl and trichloromethyl .
The content of a biphenyl phosphate compound repre¬ sented by formula (1) , which is used according to the present invention, is preferably 0.2 to 5.0 parts by mass per 100 parts by mass of the resin solid fraction of a white base coat. There is particularly preferably 0.8 to 4.5 parts by mass.
When the biphenyl phosphate compound content is less than 0.2 parts by mass, the effect to control yellowing of coated films is inadequate; and, when it exceeds 5.0 parts by mass, the water resistance and moisture resistance of coated films are poor.
[0024]
Examples of additives which may be used for coating materials are: ultraviolet absorbents, such as benzo- triazole and oxanilide-based compounds, antioxidants, such as benzophenol-based compounds, leveling agents, such as silicone-based compounds, waxes, viscosity regulators, such as organobentonites and curing catalysts.
Solvents may be compounded into the white base coating material compositions, as required. Examples which may be given of the solvents are aliphatic hydrocarbon- based solvents and aromatic hydrocarbon-based solvents. The solvent content is selected so that it is within a suitable range whereby the viscosity of the coating material is such that it may be coated.
There is no particular restriction on the coating process for the white base coating material compositions, for example, coating may be by air spray application, airless spray application or electrostatic application, but it is preferable to use electrostatic application when coating onto the surface of a conductive primer. [0025]
There is no particular restriction on the thickness of coated films of white base coating materials according to the present invention, but, in order to cover the primers and obtain the desired L values, it is preferable to have a hardened coated film thickness of 5 to 50 μm, particularly preferably 6 to 25 μm.
The resin components of the light-colored mica base coating material compositions which are used according to the present invention are preferably thermosetting resin compositions similar to the white base coating material compositions and it is particularly preferable to have combinations of base resins having cross- linkable functional groups such as hydroxyl groups, for example: acrylic resins, polyester resins, alkyd resins and urethane resins and of resins for cross-linking, such as melamine resins and block polyisocyanate compounds .
[0026]
The mica pigments used according to the present invention have white pearl pigments and/or silver pearl pigments as indispensable components and colored mica pigments, colored pigments, extender pigments and dyes may be used as required.
In general, the pigments termed "white pearl pigments" and "silver pearl" pigments are in the form of flake mica powder coated with titanium dioxide. The quantities to compound of titanium dioxide-coated flake mica powder in mica base coating materials are preferably 3 to 20 parts by mass, particularly preferably 5 to 12 parts by mass, per 100 parts by mass of solid resin fraction. [0027]
There is no particular restriction on the coating process for the mica base coating material compo¬ sitions, but it is preferable to use electrostatic coating, in a similar manner to the white base coating material compositions. There is no particular restriction on the thickness of coated films of mica base coating material materials, but the hardened coated film thickness is preferably 10 to 30 μm.
The resin components of the clear coating materials used according to the present invention are preferably thermosetting resin compositions, similar to the white base compositions and it is particularly preferable to have combinations of base resins having cross-linkable functional groups such as hydroxyl groups, for example: acrylic resins, polyester resins, alkyd resins and urethane resins and of resins for cross-linking, such as melamine resins and block polyisocyanate compounds.
[0028]
Solvents may also be compounded into the conductive primers, mica base coating material compositions and clear coating materials, as required. Examples of the solvents which may be given are organic solvents, such as aromatic hydrocarbon solvents, for instance, toluene and xylene; ketone solvents, for instance, acetone and methyl ethyl ketone; ester solvents, for instance, ethyl acetate and butyl cellosolve,- and alcohol solvents, or mixtures thereof. The solvent content is selected so that it is in a suitable range for the viscosity of the coating material to enable coating.
The process for the formation of several coated films used according to the invention can further promote the design properties, finished appearance, weather resistance, chemical resistance, water resistance, moisture resistance, and the like, of the coated films, by the application of a conductive primer to a polyolefin substrate and drying, after which a white base coating material composition, mica base coating material composition, clear coating material are applied in turn by means of a wet on wet technique and baked.
There is no particular restriction on the coating process for the clear coating material, but it is preferable to use electrostatic coating, in a similar manner to that for the white base coating material and the mica base coating material. There is no particular restriction on the thickness of coated films of clear coating materials, but the hardened coated film thick¬ ness is preferably 15 to 50 μm.
[0029]
It is preferable, for there to be sufficient hardening of coated films, to have heating to a hardening temperature of 70° to 1500C. When the hardening temperature is less than 700C, there is a risk that hardening will not proceed sufficiently. When the hardening temperature exceeds 1500C, there is a risk of incurring impaired physical properties of coated films, such as deformation or yellowing of the materials and formation of rigid and brittle coated films. The hardening time varies with the hardening temperature: suitable times are 10 to 60 minutes at a hardening temperature of 70° to 15O0C.
[Examples] [0030]
The present invention will be described more concretely by means of Examples of its execution and Comparative Examples. However, the scope of the present invention will not be limited in any way by these examples. In all the examples, except where specifically mentioned, "parts" represent parts by mass.
[0031] Manufacture of White Base Coating Material Composition 1> An acrylic resin (128 parts by mass; manufactured by BASF Coatings Japan Limited; Trade Name "LB-9020"; heating residue, 55% by mass; hydroxyl value, 56 mg KOH/g) ; titanium dioxide (80 parts by mass) ; 9,10-di- hydro-9-oxa-10-phosphaphenanthrene-10-oxide (2.6 parts by mass) ; xylene (20 parts by mass) and butyl acetate (20 parts by mass) were mixed and dispersed in a sand mill until the particle size was not more than 10 μm. The mixture was then taken out of the container, after which there were added: an amino resin [50 parts by mass; manufactured by Mitsui Kagaku (K. K.) (Mitsui Chemicals Incorporated) ; Trade Name "Yuban 122"; a butylated melamine resin; heating residue, 60% by mass] and a flow control agent (0.5 part by mass; manufactured by Monsanto; Trade Name "Modaflow" ; acrylic copolymer; heating residue, 100% by mass) , these were mixed until homogeneous, so producing White Base Coating Material Composition 1.
[0032]
<Manufacture of White Base Coating Material Compo¬ sitions 2 to 9>
White Base coating material compositions 2 to 9 were manufactured in a similar manner to White Base coating material composition 1, with the exceptions to the proportions of the mixtures listed in Table 1 and Table 2. [0033] [Table 1]
Figure imgf000017_0001
[0034] [Table 2]
Figure imgf000018_0001
[0035] Notes for Table 1 and Table 2
Note 1) Biphenyl phosphate compound HCA [manufactured by Sanko Kagaku (K K) (Sanko Chemical Company Limited); 9, 10-dihydro-9-oxa-10-phosphaphenan- threne-10-oxide) Note 2) Phosphorus-based antioxidant: Adekastab [manufactured by Asahi Denka Kogyo K K; tris(2,4-di-tertiary-butylphenyl)phosphate] Note 3) Hindered phenol: Sumilizer GA-80 [manufactured by Sumitomo Kagaku (K K) (Sumitomo Chemical Company Limited); 3, 9-bis{l,l-dimethyl-2- [β- (3- tertiary-butyl-4-hydroxy-5-methylphenyl)propionyloxy] 2,4,8,10-tetraoxa- spiro[5,5] -undecane}
[0036]
Manufacture of Mica Base Coating Material Composition
A mixture was made of: an acrylic resin (100 parts by mass; manufactured by BASF Coatings Japan Limited; Trade Name "LB-9020"; heating residue, 55% by mass; hydroxyl value, 56 mg KOH/g) ; an amino resin [20 parts by mass; manufactured by Mitsui Kagaku (K. K.) ; Trade Name "Yuban 122" ; butylated melamine resin; heating residue, 60% by mass] ; rheology control agent (20 parts by mass; manufactured by BASF Coatings Japan Limited; Trade Name "LC-0988"; inorganic base, heating residue 10% by mass) ; mica (3.7 parts by weight; flake mica powder coated with titanium dioxide, manufactured by Merck Japan; Iriojin 103 WS; heating residue 100% by mass); flow control agent (0.5 part by mass; manufactured by Monsanto; Trade Name "Modaflow") ; xylene (20 parts by mass) and butyl acetate (20 parts by mass) ; the mixture was agitated for 10 minutes in a disperser to make it uniform, so producing the mica base coating material composition.
[0037]
<Example 1>
Dirt and dust were removed from a commercial black polypropylene sheet (length, 70 mm; width, 150 mm; thickness, 3 mm) by wiping the surface of this material to be coated with isopropyl alcohol . A chlorinated polypropylene resin-based conductive primer (manufac¬ tured by BASF Coatings Japan Limited; Trade Name Puraimakku 1501) ; conductive material, conductive carbon, content of conductive material, 1 to 5 parts by mass; MSDS display) , which had its viscosity adjusted so that it was 11 seconds, under the conditions, a Ford Cup with a Number 4 orifice, at 200C, was applied, in xylene, with an air spray, so that the dried coated film thickness was 6 to 8 μm. For setting, the material was kept at room temperature for 2 minutes, after which White Base Coating Material Composition 1, which had had its viscosity adjusted so that it was 15 seconds, under the conditions, a Ford Cup with a Number 4 orifice, at 2O0C, was electrostatically applied, such that the dried coated film thickness was 15 μm.
[0038] Next, for the wet on wet process, the viscosity of a mica base coating material (amount compounded of titanium dioxide coated flake mica powder, 5.5 parts by mass to 100 parts by mass of solid resin component) was adjusted so that it was 15 seconds, under the conditions, a Ford Cup with a Number 4 orifice, at
2O0C, this was coated by means of electrostatic coating so that the dried coated film thickness was 15 μm then, for the wet on wet process electrostatic coating was carried out of a clear acrylic resin-based coating material (manufactured by BASF Coatings Japan Limited; Trade Name Puraimakku 5900 Clear; clear coating material) , so that the dried coated film thickness was 30 μm and a coated test piece was obtained by keeping the coated material for 20 minutes at 120°C; to dry it.
[0039] <Examples 2 to 4, Comparative Examples 1 to 5>
These were carried out in a similar manner to that for Example 1, changing just the white base coats to those listed in Table 1 and Table 2; test plates were prepared and tests were carried out.
Coating performance tests were carried out using these test plates. The results of appraisals are given in Table 3.
[0040]
(Adhesion of Coated Films)
Eleven notches along the length and width were made with a cutting knife in the test pieces so that one hundred 2 mm spaces were obtained and the peeling state was appraised by means of cellophane tape. The results of the appraisals were as follows:
O : no coated film has become unstuck (100/100, repre¬ sented by intersections on a Go board (i.e. a grid)) Δ: some coated film has become unstuck (85 to 99/100, represented by intersections on a Go board) x: almost all the coated film has become unstuck (0 to 84/100, represented by intersections on a Go board)
[0041]
(Resistance to Thermal Yellowing) Test boards were kept at for 90 days in a dryer set at a temperature of 8O0C, taken out and their b values determined after 1 hour with a CR-200 colorimeter [manufactured by Minolta (K K) ] . A value of 2 or less for the appraisal of yellowing (Δb) was good: it was preferable to have the numerical values as low as possible.
Yellowing (Δb) was calculated from the following relationship:
Δb = (b value after thermal resistance test) - (b value before thermal resistance test)
[0042]
(Water Resistance)
A thermostatic water bath (set temperature 35°C) fitted with a stirrer was filled with deionized water and test plates were immersed in it for 240 hours. Water was removed from the test plates with paper towels, the plates were kept at room temperature for 1 hour, after which the adhesive properties of the coated films were appraised. The results of the appraisals were the same for the adhesive properties of the above-mentioned coated films.
(Moisture Resistance)
Using a moisture resistance measuring device in conformity with JIS (Japanese Industrial Standard) K5600-7-2) moisture resistance tests were carried out for 240 hours. The test plates were taken out, surface water was removed with paper towels and the plates were kept at room temperature for 1 hour, after which the adhesive properties of the coated films were appraised. The results of the appraisals were the same for the adhesive properties of the above-mentioned coated films. [0043] [Table 3]
Figure imgf000022_0001

Claims

Patent Claims
1. White base coating material compositions, characterized in that they are the white base coating materials containing titanium oxide in a process wherein these white base coating materials are applied onto a coated film formed by coating a film of a conductive primer onto a polyolefin substrate and drying; a light-colored mica base coating material is coated onto the white base coating material by a wet on wet technique; and a clear coating material is coated onto the mica base coating material by a wet on wet technique, after which a coated film is formed by thermal hardening in a three-coat one-bake procedure; the compositions contain 0.2 to 5.0 parts by mass of a biphenyl phosphate compound represented by formula (1) per 100 parts by mass of the solid resin fraction.
[Chemical Expression 1]
Figure imgf000023_0001
H
(in which formula: R1 and R2 each independently represent a hydrogen atom, halogen atom, a hydrocarbon of 1 to 6 carbon atoms, or a halogenated hydrocarbon of 1 to 6 carbon atoms; and m and n represent integers from 0 to 4. )
2. The white base coating material compositions, as claimed in claim 1, characterized in that R1 and R2 in the biphenyl phosphate represented by formula (1) are both hydrogen atoms.
3. A process for the formation of coated films characterized in that: a white base coating material, as claimed in claim 1 or 2, is applied onto a coated film, formed by coating a conductive primer onto a polyolefin substrate and drying; a mica base coating material is coated onto the white base coating material by a wet on wet technique; and a clear coating material is coated onto this mica base coating material by means of a wet on wet technique, after which a coated film is formed by thermal hardening in a three-coat one-bake procedure.
4. Coated products characterized in that coating has been carried out by means of the coating formation process as claimed in claim 3.
PCT/IB2005/003186 2004-10-28 2005-10-26 White basecoat coating composition, method for forming coating film and coated article WO2006046117A1 (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016023760A1 (en) * 2014-08-11 2016-02-18 Lisa Dräxlmaier GmbH Coated substrate and method for the production thereof
US11808833B2 (en) 2016-10-28 2023-11-07 Ppg Industries Ohio, Inc. Coatings for increasing near-infrared detection distances
US11809933B2 (en) 2018-11-13 2023-11-07 Ppg Industries Ohio, Inc. Method of detecting a concealed pattern
US12001034B2 (en) 2022-11-04 2024-06-04 Ppg Industries Ohio, Inc. Near infrared control coating, articles formed therefrom, and methods of making the same

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JPS58127742A (en) * 1982-01-26 1983-07-29 Sanko Kagaku Kk Electrically conductive resin blend composition
JPS58145769A (en) * 1982-02-23 1983-08-30 Takeda Chem Ind Ltd Conductive coating
JPS5922938A (en) * 1982-07-28 1984-02-06 Sanko Kagaku Kk Electrically conductive resin composition
JPS61231063A (en) * 1985-04-05 1986-10-15 Toshiba Chem Corp Electrically conductive paint
JPH0940905A (en) * 1995-07-31 1997-02-10 Asahi Chem Ind Co Ltd Hardly discoloring coating composition
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JPS54156041A (en) * 1978-05-31 1979-12-08 Showa Electric Wire & Cable Co Ltd Refractory coating compound
JPS58127742A (en) * 1982-01-26 1983-07-29 Sanko Kagaku Kk Electrically conductive resin blend composition
JPS58145769A (en) * 1982-02-23 1983-08-30 Takeda Chem Ind Ltd Conductive coating
JPS5922938A (en) * 1982-07-28 1984-02-06 Sanko Kagaku Kk Electrically conductive resin composition
JPS61231063A (en) * 1985-04-05 1986-10-15 Toshiba Chem Corp Electrically conductive paint
JPH0940905A (en) * 1995-07-31 1997-02-10 Asahi Chem Ind Co Ltd Hardly discoloring coating composition
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016023760A1 (en) * 2014-08-11 2016-02-18 Lisa Dräxlmaier GmbH Coated substrate and method for the production thereof
US11808833B2 (en) 2016-10-28 2023-11-07 Ppg Industries Ohio, Inc. Coatings for increasing near-infrared detection distances
US11977154B2 (en) 2016-10-28 2024-05-07 Ppg Industries Ohio, Inc. Coatings for increasing near-infrared detection distances
US11809933B2 (en) 2018-11-13 2023-11-07 Ppg Industries Ohio, Inc. Method of detecting a concealed pattern
US12001034B2 (en) 2022-11-04 2024-06-04 Ppg Industries Ohio, Inc. Near infrared control coating, articles formed therefrom, and methods of making the same

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