[go: up one dir, main page]

WO2017002885A1 - Film de revêtement composite à couche de surface pelable, composition de revêtement pour former le film de revêtement composite et procédé - Google Patents

Film de revêtement composite à couche de surface pelable, composition de revêtement pour former le film de revêtement composite et procédé Download PDF

Info

Publication number
WO2017002885A1
WO2017002885A1 PCT/JP2016/069349 JP2016069349W WO2017002885A1 WO 2017002885 A1 WO2017002885 A1 WO 2017002885A1 JP 2016069349 W JP2016069349 W JP 2016069349W WO 2017002885 A1 WO2017002885 A1 WO 2017002885A1
Authority
WO
WIPO (PCT)
Prior art keywords
coating
layer
dryer
coating film
inner layer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2016/069349
Other languages
English (en)
Japanese (ja)
Inventor
健吾 卜部
充香 井賀
康学 湊
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Paint Holdings Co Ltd
Original Assignee
Nippon Paint Holdings Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nippon Paint Holdings Co Ltd filed Critical Nippon Paint Holdings Co Ltd
Priority to CN201680050768.7A priority Critical patent/CN107922784B/zh
Priority to EP16817993.5A priority patent/EP3318615B1/fr
Priority to US15/740,093 priority patent/US10538676B2/en
Priority claimed from JP2016128592A external-priority patent/JP6746400B2/ja
Publication of WO2017002885A1 publication Critical patent/WO2017002885A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

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
    • B05D7/24—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 for applying particular liquids or other fluent materials
    • 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
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/20—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for coatings strippable as coherent films, e.g. temporary coatings strippable as coherent films
    • 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

Definitions

  • the present invention provides a surface-peelable composite coating, a coating composition for forming such a composite coating, and a method thereof.
  • An alkyd resin is an oxidative polymerizable resin synthesized from a polybasic acid or polybasic acid anhydride, a polyhydric alcohol, and a fatty acid.
  • the oxidative polymerizable resin undergoes ester oxidative polymerization with oxygen in the air at room temperature.
  • a three-dimensional network structure is formed, and a coating film having excellent solvent resistance and water resistance is obtained.
  • Alkyd resin-based paints can be used for various materials, and because they are inexpensive, they are useful for a wide range of applications from indoor wall painting to painting of large structures such as buildings, ships, and vehicles. .
  • Patent Document 1 discloses a resin composition and a coating material that are useful as civil engineering and building materials that retain low-temperature flexibility and are excellent in low-temperature curability, and that are radically cured.
  • This resin composition contains (A) a polyether acrylic urethane resin, (B) an air-drying imparting polymer using a drying oil and / or a fatty acid compound thereof, and (C) an ethylenically unsaturated monomer. To do.
  • the component (B) is preferably an alkyd resin.
  • paraffin and / or wax (D) may be used in combination for the purpose of improving the drying property.
  • Patent Document 2 discloses a resin composition and a covering material that are suitable for a wide range of civil engineering and building material applications and are radically cured, as in Patent Document 1.
  • This resin composition comprises (A) a resin having a (meth) acryloyl group at the molecular end, (B) an air-drying imparting polymer using a drying oil and / or a fatty acid compound thereof, and (C) a molecular weight of 160 or more.
  • the ethylenically unsaturated monomer which has the (meth) acryloyl group of this is contained.
  • the component (B) is preferably an alkyd resin.
  • paraffin and / or wax (D) may be used in combination for the purpose of improving the drying property.
  • Patent document 3 discloses a coating composition having a thermosetting film-forming property and based on a wax or a wax-like compound (for example, polyethylene wax, paraffin wax, etc.) or a natural drying oil or an alkyd resin.
  • This coating composition is used to prevent corrosion of the metal substrate of the car body and is an additive that gels at relatively high temperatures (eg, C 1-8 alkyl esters of polyvinyl chloride, methacrylic acid or acrylic acid) Etc.) can be completely prevented from flowing or dripping.
  • the conventional general coating film is designed to be completely cured, if the coating film surface is damaged, contaminated, or deactivated, difficult re-painting is essential.
  • the present inventors have used a specific coating composition containing a flow suppression and polymerization reaction inhibitor, a dryer and an oxidation polymerization inhibitor in the oxidation polymerizable resin. It has been found that a composite coating film comprising a cured film layer and an uncured inner layer can be formed. The film layer of the composite coating film can be peeled off, and the surface of the uncured inner layer that appears by peeling is exposed to oxygen, and the surface layer is dried and cured to form a new film layer.
  • the present invention includes a base resin composition comprising an oxidatively polymerizable resin; an organic compound having a melting point of 5 to 150 ° C .; a dryer; and an oxidative polymerization inhibitor comprising at least one of a dryer protective agent and a radical inhibitor.
  • a coating composition is provided.
  • the present invention is a composite coating film comprising a coating layer and an inner layer
  • the inner layer is an uncured body of the coating composition of the present invention
  • the coating layer is a cured body of the coating composition formed so as to be peelable on the surface of the inner layer
  • a composite coating film in which a surface layer of an inner layer exposed to air by peeling of the coating layer formed on the inner layer is cured by oxidative polymerization so that another coating layer can be peeled off.
  • the present invention is a method for producing a composite coating film comprising a coating layer and an inner layer, wherein the coating layer is detachably formed on the surface of the inner layer, Applying the coating composition of the present invention on a substrate to form a coating film made of an uncured body of the coating composition; and exposing the coating film made of the uncured body to the surface thereof by air exposure
  • a method for producing a composite coating film comprising the steps of: curing by oxidative polymerization to form the coating layer, and maintaining the portion under the coating layer in an uncured state to form an inner layer.
  • the composite coating according to the present invention can be formed by applying the coating composition of the present invention on a substrate and exposing it to oxygen in the air, when the surface is damaged or contaminated, or applied When the performed function is deactivated, the surface layer can be updated once or a plurality of times by peeling only the coating layer.
  • the composite coating film according to the present invention can be used as a lower layer, and a top coating can be applied thereon, or an upper material can be formed by applying interior materials such as exterior materials and wallpaper materials.
  • the upper layer can be easily updated by peeling.
  • the coating composition of the present invention comprises at least one of a base resin composition containing an oxidation polymerizable resin; an organic compound having a melting point of 5 to 150 ° C .; a dryer; and a dryer protective agent and a radical inhibitor.
  • the organic compound is contained in an amount of 10 to 100% by weight with respect to 100% by weight of the base resin composition and 100% by weight of the solid content of the oxidative polymerizable resin.
  • the oxidative polymerization inhibitor includes any one of a dryer protective agent and a radical inhibitor, Containing from 0.5 to 4 moles of the dryer protective agent per mole of metal elements in the dryer; or Containing 0.01 to 2.0% by weight of the radical inhibitor with respect to 100% by weight of the oxidative polymerizable resin solid content; or
  • the oxidative polymerization inhibitor includes both a dryer protective agent and a radical inhibitor
  • the dryer protective agent is contained in an amount of 0.5 to 4 moles per mole of the metal element in the dryer
  • the radical inhibitor is contained in an amount of 2.0% by weight or less based on 100% by weight of the oxidative polymerizable resin solid content.
  • the radical inhibitor is added in an amount of 0.01 to 2.0 wt. % Is included.
  • the base resin composition is a resin composition containing at least an oxidation polymerizable resin, and may further contain an oxidation polymerizable compound and a coating resin not having an oxidation polymerizable group.
  • the oxidatively polymerizable resin contained in the base resin composition is a resin containing an oxidatively polymerizable group that undergoes an oxidative polymerization reaction through a reaction with oxygen in the air and three-dimensionally crosslinks, and is not limited.
  • alkyd resin which is a reaction product of polybasic acid or polybasic acid anhydride, fatty acid and polyhydric alcohol, reaction product of acrylic resin or urethane resin and fatty acid, and the like can be mentioned.
  • polybasic acid or polybasic acid anhydride in the alkyd resin examples include, but are not limited to, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, itaconic acid, maleic acid Dicarboxylic acids such as fumaric acid, phthalic acid, isophthalic acid and terephthalic acid; tricarboxylic acids such as trimellitic acid; and compounds having two or more carboxyl groups in the molecule such as tetracarboxylic acid such as pyromellitic acid and their An acid anhydride is mentioned.
  • the fatty acid in the alkyd resin that can be used in the present invention is not limited, and for example, an iodine value of 130 selected from the group consisting of linseed oil, tung oil, poppy oil, perilla oil, sesame oil, sunflower oil and safflower oil.
  • Fatty acids contained in the above dry oils fatty acids contained in semi-dry oils having an iodine value of 100 to 130 selected from the group consisting of soybean oil, rice bran oil, cottonseed oil, sesame oil; olive oil, almond oil, peanut oil, coconut oil , Fatty acids contained in non-drying oils having an iodine value of less than 100, selected from the group consisting of coconut oil, rapeseed oil and castor oil.
  • Examples of such fatty acids include, but are not limited to, unsaturated fatty acids such as palmitoleic acid, oleic acid, linoleic acid, and linolenic acid.
  • polyhydric alcohol in the alkyd resin examples include, but are not limited to, ethylene glycol, diethylene glycol, propylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,2-diethyl-1,3-propanediol, neopentyl Diols selected from the group consisting of glycols; and trivalent or higher valent polyols selected from the group consisting of triethylene glycol, trimethylolpropane, trimethylolethane, glycerin, pentaerythritol, and 2,2-dimethylolpropion Acid, 2, - dimethylol butanoic acid, 2,2-di
  • the fatty acid in the reaction product of an acrylic resin or urethane resin and a fatty acid that can be used in the present invention is the same as the fatty acid in the alkyd resin that can be used in the present invention.
  • the solid content of the oxidatively polymerizable resin is 70 to 100% by weight, preferably 85 to 100% by weight, more preferably 95 to 100% by weight, based on the solid content of the entire base resin composition. If content of the said oxidation polymerizable resin exists in the said range, the dryness of a coating film is ensured.
  • the oxidatively polymerizable compound that may be contained in the base resin composition is a compound containing an oxidatively polymerizable group that undergoes oxidative polymerization reaction through three-dimensional crosslinking by reaction with oxygen in the air.
  • Examples include fatty acids contained in semi-drying oils having an iodine value of 100 to 130 selected from the group consisting of rice bran oil, cottonseed oil, and sesame oil.
  • examples of such fatty acids include, but are not limited to, unsaturated fatty acids such as palmitoleic acid, oleic acid, linoleic acid, and linolenic acid.
  • the coating resin that does not have an oxidizable polymerizable group that may be contained in the base resin composition is a general coating resin including an acrylic resin, a urethane resin, an epoxy resin, a polyester resin, and the like. .
  • an organic compound having a melting point of 5 to 150 ° C. can be kneaded with the base resin composition at a temperature equal to or higher than the melting point, and the resulting mixture is fluidized at the use environment temperature of the coating film. It is a compound which forms a coating film structure without doing. That is, the inner layer, which is an uncured body of the composite coating film, can form and maintain a coating film structure without flowing in the use environment by the action of the organic compound. Moreover, by interposing between each component of oxidatively polymerizable resin, it has the function to prevent the dry hardening reaction by an oxidative polymerization reaction by interfering with the proximity of the oxidatively polymerizable resins.
  • the organic compound can be said to be a substance for suppressing flow and polymerization reaction.
  • the melting point of the organic compound when the melting point of the organic compound is 5 ° C. or higher, a coating film structure can be formed in a normal use environment or the like. If the melting point is 150 ° C. or lower, it is not necessary to heat excessively when kneading with the base resin composition.
  • Examples of the organic compound that can be used in the present invention include, but are not limited to, liquid paraffin, paraffin wax, microcrystalline wax, polyethylene, polyacrylamide, polyacrylate, animal wax, vegetable wax, higher fatty acid, higher alcohol. , Amines, ketones, esters and the like. These organic compounds can be used alone or in admixture of two or more. Paraffins are alkanes represented by C n H 2n + 2 , and include liquids and solids at room temperature depending on the carbon number or molecular weight. The liquid one is called liquid paraffin, and the solid one is called paraffin wax. Paraffin wax is generally classified by its melting point rather than carbon number or molecular weight.
  • Paraffin wax includes, for example, those having a low melting point (about 42 ° C.) to a high melting point (about 70 ° C.) and those having a higher melting point.
  • paraffin wax, polyethylene or a combination thereof is preferred.
  • the content of the organic compound is preferably 10 to 100% by weight with respect to 100% by weight of the base resin composition.
  • the content is less than the lower limit, it is weak against temperature changes in the use environment, and when it is more than the upper limit, it takes time to form the coating layer.
  • the content is more preferably 15 to 50% by weight, and further preferably 20 to 40% by weight.
  • a dryer is a compound that accelerates the oxidative polymerization of an oxidative polymerizable resin such as an alkyd resin, and mainly generates peroxide by hydrogen abstraction of ⁇ -methylene groups of double bonds in the presence of oxygen, It promotes the generation of oxygen radicals by decomposition of the generated peroxide.
  • Polymerization proceeds by radical chain reaction to form a coating film having a three-dimensional network structure.
  • the dryer that can be used in the present invention includes a metal soap composed of a bond of a metal and a long-chain fatty acid.
  • the metal that can be used for the metal soap is not limited, but examples include metals such as cobalt, barium, vanadium, manganese, cerium, lead, iron, calcium, zinc, zirconium, nickel, tin, and strontium, preferably Cobalt and manganese excellent in surface drying properties, and more preferably cobalt.
  • the long chain fatty acid that can be used for the metal soap is not limited, and examples thereof include organic acids such as propionic acid, octylic acid, naphthenic acid, neodecanoic acid, tung oil acid, linseed oil acid, soybean oil acid, and resin acid.
  • Propionic acid, naphthenic acid and octylic acid are preferred, and naphthenic acid and octylic acid are more preferred.
  • the metal soap that can be used in the present invention is preferably a cobalt salt of naphthenic acid or octylic acid, and more preferably a cobalt salt of naphthenic acid.
  • the content of the dryer is preferably such that the content of the metal element in the dryer is 0.001 to 1.5% by weight based on 100% by weight of the solid content of the oxidative polymerizable resin.
  • the content is less than the lower limit, it takes time to form the coating layer.
  • the content is more than the upper limit, poor appearance such as itchiness tends to occur in the coating layer.
  • the content is more preferably 0.01 to 1.0% by weight, and still more preferably 0.05 to 0.5% by weight.
  • the oxidative polymerization inhibitor is an agent in which the oxidative polymerizable resin and the oxidative polymerizable compound contained in the base resin composition suppress an oxidative polymerization reaction due to a reaction with oxygen in the air, and a dryer protective agent. And radical inhibitors.
  • the dryer protective agent and the radical inhibitor can be used alone or in combination.
  • the dryer protective agent is a substance that inhibits the oxidative polymerization promoting effect of the dryer by coexistence with the dryer. Since the volatile dryer protective agent is used in the coating composition of the present invention, the dryer protective agent disappears due to volatilization near the surface of the coating film, and the effect of promoting the oxidative polymerization of the dryer is exhibited. Thereby, only the surface layer of the coating film is cured to form the coating layer. Since this coating layer suppresses volatilization of the internal dryer protective agent and inhibits the oxidative polymerization promoting effect of the dryer, the internal layer is maintained in an uncured state.
  • the dryer protective agent that can be used in the present invention is a volatile substance having a boiling point of 300 ° C. or lower, and is not limited to, for example, methyl ethyl ketoxime, acetone oxime, butyl aldoxime, cyclohexanone oxime, dialkylhydroxylamine, ammonia, Examples include hydroxylamine, triethylamine, dimethylethanolamine and the like. Methyl ethyl ketoxime and cyclohexanone oxime are preferred.
  • the content of the dryer protective agent is preferably 0.5 to 4 mol with respect to 1 mol of the metal element in the dryer.
  • the content is less than the lower limit, the coating layer becomes thick, and when it is more than the upper limit, it takes time to form the coating layer.
  • the amount is more preferably 1 to 3 mol, and further preferably 1.5 to 2.5 mol.
  • the total amount should just be in the said range.
  • the radical inhibitor is not a substance that inhibits the oxidative polymerization promotion of the dryer, but a substance that directly suppresses the oxidative polymerization initiation function of radicals existing in the system, unlike the dryer protective agent. Since the volatile radical inhibitor is used in the coating composition of the present invention, the radical inhibitor disappears due to volatilization near the surface of the coating film, and the radical oxidative polymerization initiation function is exhibited. Thereby, only the surface layer of the coating film is cured to form the coating layer. Since this coating layer suppresses volatilization of the internal radical inhibitor and inhibits the radical oxidative polymerization initiation function, the internal layer is maintained in an uncured state.
  • the radical inhibitor that can be used in the present invention is a volatile substance having a boiling point of 300 ° C. or less, and includes, but is not limited to, phenolic substances such as eugenol, butylated hydroxytoluene, butylated hydroxyanisole; Examples thereof include phosphite substances such as trimethyl phosphite, triethyl phosphite, and tributyl phosphite. Eugenol and tributyl phosphite are preferred.
  • the content of the radical inhibitor is preferably 0.01 to 2.0% by weight with respect to 100% by weight of the oxidative polymerizable resin solid content.
  • the content is less than the lower limit, the coating layer becomes thick, and when it is more than the upper limit, it takes time to form the coating layer.
  • it is more preferably 0.03 to 1.0% by weight, still more preferably 0.05 to 0.5% by weight.
  • the total amount may be within the above range.
  • the dryer protective agent is in a range of 4 mol or less with respect to 1 mol of the metal element in the dryer, and the radical inhibitor is 100% by weight of the oxidative polymerizable resin solid content. It can be contained in the range of 2.0% by weight or less.
  • the dryer protective agent is in a range of less than 0.5 mol with respect to 1 mol of the metal element in the dryer, and the radical inhibitor is less than 0.01 wt% with respect to 100 wt% of the oxidative polymerizable resin solid content. In this range, the effect of inhibiting oxidative polymerization cannot be sufficiently exerted, and is excluded.
  • the coating composition of the present invention has the composition described above, and is applied onto a substrate to form a coating film composed of an uncured body of the coating composition. It can be cured by oxidative polymerization to form a composite coating film comprising a cured coating layer and an uncured inner layer under the coating layer. Moreover, since the inner layer of the obtained composite coating film is maintained in an uncured state, the coating layer can be peeled off, and the surface layer of the inner layer exposed to air by the peeling of the coating layer is cured by oxidative polymerization. Then, another film layer is newly formed. As long as there is an uncured inner layer, the surface layer of the coating film can be renewed by peeling the coating layer many times.
  • a pigment component can usually be added to the coating composition of the present invention.
  • pigment components that can be used in the present invention include, but are not limited to, for example, colored pigments such as titanium dioxide, carbon black, petal, phthalocyanine blue, extender pigments such as calcium carbonate, talc, mica, and clay, and further anti-rust pigments. Etc.
  • the content of the pigment component in the coating is preferably 0.1 to 70%, more preferably 0.1 to 50% in terms of pigment weight concentration (PWC) based on the solid content of the coating composition. If the PWC is too low, the coating film may not be sufficiently concealed. If the PWC is too high, it may be difficult to form a coating layer.
  • PWC pigment weight concentration
  • the coating composition of the present invention may further contain a commonly used coating additive.
  • paint additives that can be used in the paint composition of the present invention include, but are not limited to, ultraviolet absorbers, light stabilizers, viscosity modifiers, surface modifiers, antioxidants, fungicides, and algae inhibitors. , Plasticizers, antifoaming agents and the like.
  • the coating additive is usually used in an amount of 0.01 to 10% by weight based on 100% by weight of the coating composition.
  • the coating composition of the present invention can also contain an organic solvent as long as the effects of the present invention are not affected.
  • the composite coating of the present invention is a composite coating consisting of a coating layer 3 and an inner layer 2 formed using the coating composition of the present invention as shown in FIG.
  • the coating layer 3 formed in the above can be peeled off.
  • the surface layer of the inner layer 2 that has appeared due to the peeling of the coating layer 3 is exposed to air and cured by oxidative polymerization to form a new coating layer 3 separately.
  • any appropriate method can be adopted depending on the type of the substrate. Although it does not specifically limit, Application
  • the inner layer 2 is an uncured body of the coating composition of the present invention, and the coating layer 3 is formed on the surface of the inner layer 2 so as to be peelable. It is a cured product of the product. Thus, since only the coating layer 3 is cured, it can be peeled off, and since the inner layer 2 is not cured, the surface layer of the inner layer 2 exposed to air by the peeling of the coating layer 3 is cured, The surface layer of the coating can be updated (FIG. 1).
  • the coating layer 3 is formed when it is determined that the coating layer is surface-dried in a 23 ° C. atmosphere in accordance with the provisions of JIS K5600-3-2 (the Barotini method described later). Judge that it was done.
  • the inner layer In the composite coating film of the present invention, the inner layer must be maintained in an uncured state. Therefore, it is necessary to confirm that the inner layer of the composite coating film in which the coating layer is formed is uncured.
  • a rubber ball is dropped on the composite coating film, and the rebound resilience is determined from the rebound height of the ball.
  • the impact resilience at 23 ° C. is 11 to 55%, it is determined that the inner layer is uncured. Even if the impact resilience is in the above range, if it is out of the range, it means that the curing of the inner layer is proceeding. That is, once the impact resilience in the above range is shown, it is desirable that the impact resilience after being exposed to air for a long time, for example after being exposed to air at 23 ° C. for 6 months, is in the above range.
  • the thickness of the coating layer 3 is in the range of 10 ⁇ m to 5 mm.
  • a coating layer 3 having a thickness in the range of 10 ⁇ m to 5 mm is newly formed on the surface layer of the inner layer 2, so that the inner layer 2 is equal to or more than the thickness of the coating layer 3 If it has thickness of this, peeling of the membrane
  • the composite coating film of the present invention can be used as a single-layer coating film, or can be used as a lower layer, and an upper coating is applied to the upper surface of the coating film, or an interior material such as an exterior material or wallpaper is applied to the upper layer. It can also be formed.
  • the interior materials such as the top coat, exterior material, and wallpaper are not particularly limited, and those that are usually used can be used.
  • the coating layer made of the uncured body is exposed to air at 5 to 150 ° C. for 1 day or 20 minutes or more to cure the surface layer by oxidative polymerization to form the coating layer 3. Since the oxidative polymerization inhibitor existing in the vicinity of the uncured surface layer volatilizes, the effect of promoting the oxidative polymerization reaction of the dryer is demonstrated, or the radical oxidative polymerization initiating function present in the system is exhibited and only the surface layer is cured. To do.
  • the inner layer 2 since an oxidative polymerization inhibitor is present in the inner layer 2 below the coating layer, the effect of promoting the oxidative polymerization reaction of the dryer is inhibited, or the oxidative polymerization initiation function of radicals present in the system is suppressed, Further, the intrusion of oxygen is prevented by the hardened surface layer. Furthermore, the inner layer 2 is maintained uncured by the effect of the organic compound that obstructs the approach between the oxidatively polymerizable resins.
  • the drying conditions can be adjusted as appropriate so that only the surface layer is cured.
  • Example 1 Preparation of coating composition [Example 1] As a preparatory stage, alkyd resin varnish (Beccosol P-470-70; DIC Corporation) is heated to 40 ° C, and paraffin (melting point 42-44 ° C) (Wako Pure Chemical Industries, Ltd.) is heated to 70 ° C. Polyethylene (Neowax L (melting point 95-115 ° C.) (Yasuhara Chemical Co., Ltd.)) was heated to 130 ° C. to be in a liquid state. While the alkyd resin varnish heated to 40 ° C. was stirred with a disper, liquid paraffin and polyethylene were mixed.
  • alkyd resin varnish Beccosol P-470-70; DIC Corporation
  • paraffin melting point 42-44 ° C
  • Polyethylene Naowax L (melting point 95-115 ° C.) (Yasuhara Chemical Co., Ltd.)
  • a dryer protective agent (2-butanone oxime (Tokyo Chemical Industry Co., Ltd.)) and a dryer (cobalt naphthenate / mineral spirit solution (Co: 6%)) (Wako Pure Chemical Industries, Ltd.) were mixed in order, and 300 rpm For 5 minutes.
  • Each component was blended according to Table 1. From the atomic weight of cobalt: 58.93 and the molecular weight of 2-butanone oxime: 87.12, the number of moles of the dryer protective agent was calculated per mole of the metal element in the dryer. After completion of the stirring, it was visually confirmed that the mixture was uniform to obtain a coating composition.
  • Example 2 Except not adding polyethylene, it mix
  • Examples 3 to 5 A coating composition was prepared in the same manner as in Example 1 except that polyethylene was not added and the ratio between the alkyd resin and the paraffin was changed and blended according to Table 1.
  • Example 9 Table except that alkyd-modified urethane resin (Burnac TD-125-HV; DIC Corporation) or acrylic resin (Acridic A-1300; DIC Corporation) is mixed into the base resin composition as a resin other than the alkyd resin.
  • the coating composition was prepared in the same manner as in Example 1.
  • Example 11 and 12 A coating composition was prepared in the same manner as in Example 1 except that paraffin (melting point: 50 to 52 ° C.) (Showa Chemical Co., Ltd.) and paraffin (melting point: 60 to 62 ° C.) (Kishida Chemical Co., Ltd.) was used. Prepared.
  • Example 13 to 15 Except for using a dryer (cobalt octoate xylene solution (Co: 6%)) (DIC Corporation) or changing the amount of dryer (cobalt naphthenate mineral spirit solution (Co: 6%)) The coating composition was prepared in the same manner as in Example 1.
  • Example 16 to 19 Except for using the dryer protective agent (cyclohexanone oxime (Wako Pure Chemical Industries, Ltd.)) or changing the addition amount of the dryer protective agent (2-butanone oxime (Tokyo Chemical Industry Co., Ltd.)), A coating composition was prepared in the same manner as in Example 1. From the atomic weight of cobalt: 58.93, the molecular weight of 2-butanone oxime: 87.12, and the molecular weight of cyclohexanone oxime: 113.16, the number of moles of the dryer protective agent was calculated per mole of the metal element in the dryer. .
  • Example 20 to 22 A coating composition was prepared in the same manner as in Example 1, except that the dryer protective agent was not added and eugenol (Wako Pure Chemical Industries, Ltd.) was added as a radical inhibitor.
  • Example 23 and 24 A coating composition was prepared in the same manner as in Example 1 except that Eugenol (Wako Pure Chemical Industries, Ltd.) or tributyl phosphite (Wako Pure Chemical Industries, Ltd.) was used in combination as a dryer protective agent and a radical inhibitor. was prepared.
  • Example 25 Mixing carbon black (MA100; Mitsubishi Chemical Corporation) and oily clay (CLAYTON R HY (BYK Additives & Instruments)) while stirring with a disper into alkyd resin varnish (Beccosol P-470-70; DIC Corporation) A premix paste was prepared and dispersed with a sand grind mill to prepare a dispersion paste.
  • paraffin melting point: 42 to 44 ° C.
  • powdered polyethylene (neo wax L (melting point: 95 to 115 ° C.) (Yasuhara Chemical Co., Ltd.)) is set to 130 ° C.
  • Example 26 Titanium oxide (Ti-PURE R-706 (DuPont Co., Ltd.)), oily clay (CLAYTON R HY (BYK Additives & Instruments)) while stirring with an dispyd in alkyd resin varnish (Beccosol P-470-70; DIC Corporation) ) To prepare a premix paste, which was dispersed with a sand grind mill to prepare a dispersion paste. As a preparatory stage, paraffin (melting point: 42 to 44 ° C.) (Wako Pure Chemical Industries, Ltd.) is set to 70 ° C.
  • powdered polyethylene (neo wax L (melting point: 95 to 115 ° C.) (Yasuhara Chemical Co., Ltd.)) is set to 130 ° C. Heated to liquid state. While the dispersion paste heated to 40 ° C. was stirred with a disper, liquid paraffin and polyethylene were mixed. Then, a dryer protective agent (2-butanone oxime (Tokyo Chemical Industry Co., Ltd.)) and a dryer (cobalt naphthenate / mineral spirit solution (Co: 6%) (Wako Pure Chemical Industries, Ltd.) were mixed in order, and 300 rpm The ingredients were blended according to Table 4. After completion of the stirring, it was visually confirmed that the mixture was uniform to obtain a coating composition.
  • a dryer protective agent (2-butanone oxime (Tokyo Chemical Industry Co., Ltd.)
  • a dryer cobalt naphthenate / mineral spirit solution (Co: 6%) (Wako Pure Chemical Industries, Ltd.)
  • Example 27 A coating composition was prepared in the same manner as in Example 1.
  • Comparative Example 2 A coating composition was prepared in the same manner as in Comparative Example 1 except that the blending ratio of paraffin to the base resin composition containing the alkyd resin varnish was increased.
  • Comparative Example 3 A coating composition was prepared in the same manner as in Comparative Example 1 without using a dryer and an oxidative polymerization inhibitor and blending them according to Table 5.
  • Comparative Example 4 A dryer was used but no oxidative polymerization inhibitor was used, and blending was carried out according to Table 5 to prepare a coating composition in the same manner as in Comparative Example 1.
  • Step 1 Each coating composition of Examples 1 to 27 and Comparative Examples 1 to 5 is placed in a dish-like container (bottom area is about 34 cm 2 ) having a radius of about 3.3 cm and a height of 2.5 mm, and a dry film thickness of 2.5. painted to mm (Fig. 2a)
  • Step 2 The prepared coating film was dried in a 23 ° C. atmosphere for one day or in a 120 ° C. atmosphere for 20 minutes to obtain a dry initial coating film (FIG. 2b).
  • Step 3 Dry in a 23 ° C. atmosphere for 6 months (FIG. 2c) and observe the change over time to confirm the formation of the desired composite coating film.
  • the coating film is composed of a viscous component and an elastic component.
  • the elastic component stores the fall energy (kinetic energy) of this test, while the viscous component loses the energy.
  • the technique of peeling multiple times is that the surface layer is reactively cured and the inside is uncured, and the key point is that the rebound resilience in this test is lower than that of a normal fully cured coating. Comparison of this value indicates that the interior is unreacted.
  • the film thickness of the coating sample A for measurement test was unified to 2.5 mm, and the influence of the film thickness was removed.
  • Rebound resilience 0 to 10%: The surface layer is not sufficiently cured.
  • Rebound resilience 56% or more: The inside is too hard.
  • (4) Internal fluidity of composite coating [Purpose] Clarify the effect of the flow inhibitory substance on the flow of the coating film. [Test conditions] In a 23 ° C. atmosphere, the prepared coated plate was tilted to 90 ° and allowed to stand for 1 hour, and then the presence or absence of flow (deformation) was visually confirmed.
  • the peeled film thickness was measured with an electronic caliper.
  • Evaluation criteria ++: When all of the coating layer can be peeled off from the inner layer without being cut off in the middle, peeling is possible. +: Even if the coating layer is cut off in the middle, finally, all of the coating layer can be peeled off from the inner layer, so that peeling is possible. -: When at least a part of the coating layer cannot be peeled off from the inner layer, the peeling is impossible.
  • any of the coating films prepared using the coating compositions of Examples 1 to 27 had an appropriate impact resilience even after 1 day at 23 ° C. or after 20 minutes at 120 ° C. and after 6 months at 23 ° C. Rate (11-55%), good surface drying and surface tackiness.
  • the internal fluidity was good after the initial coating, no cracks or wrinkles were formed on the coating film surface, and no deformation occurred.
  • the impact resilience was measured immediately after peeling the film layer of the composite coating film after 6 months using the coating compositions of Examples 1 and 2, it was 7.9% and 10.1%, respectively. It was confirmed that the inner layer was maintained in an uncured state even after 6 months of drying.
  • the coating films prepared using the coating compositions of Comparative Examples 1 to 5 lacking any of the components contained in the coating composition according to the present invention were completely cured to the inner layer by 6 months, The rebound resilience increased to about 56-70%.
  • the coating composition of the present invention is used, a composite coating film comprising a cured film layer and an uncured inner layer can be obtained, and this film layer can be peeled off and the coating film surface layer can be updated multiple times. Therefore, by applying the coating composition of the present invention, for example, even in a place where repainting is difficult, it is possible to always maintain a state free from damage or contamination, or to maintain a function imparted to the coating film. .

Landscapes

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

Abstract

La présente invention concerne un film de revêtement composite à base de résine par polymérisation oxydative, la couche de surface du film de revêtement pouvant être actualisée une pluralité de fois par pelage d'une couche de surface. Plus spécifiquement, la présente invention forme un film de revêtement composite comprenant une couche de peau durcie et une couche interne non durcie à l'aide de : une composition de résine de base comprenant une résine de polymérisation oxydative ; un composé organique ayant un point de fusion allant e 5 à 150 °C ; un séchoir ; et une composition de revêtement comprenant un inhibiteur de polymérisation oxydative comprenant au moins un élément parmi un agent de protection de séchoir et un inhibiteur de radical.
PCT/JP2016/069349 2015-07-01 2016-06-29 Film de revêtement composite à couche de surface pelable, composition de revêtement pour former le film de revêtement composite et procédé Ceased WO2017002885A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN201680050768.7A CN107922784B (zh) 2015-07-01 2016-06-29 表面层可剥离的复合涂膜、用于形成复合涂膜的涂料组合物和方法
EP16817993.5A EP3318615B1 (fr) 2015-07-01 2016-06-29 Film de revêtement composite à couche de surface pelable, composition de revêtement pour former le film de revêtement composite et procédé
US15/740,093 US10538676B2 (en) 2015-07-01 2016-06-29 Surface layer-peelable composite coating film, coating composition for forming composite coating film, and method

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2015132782 2015-07-01
JP2015-132782 2015-07-01
JP2016-128592 2016-06-29
JP2016128592A JP6746400B2 (ja) 2015-07-01 2016-06-29 表層剥離可能な複合塗膜、複合塗膜を形成するための塗料組成物および方法

Publications (1)

Publication Number Publication Date
WO2017002885A1 true WO2017002885A1 (fr) 2017-01-05

Family

ID=57608744

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2016/069349 Ceased WO2017002885A1 (fr) 2015-07-01 2016-06-29 Film de revêtement composite à couche de surface pelable, composition de revêtement pour former le film de revêtement composite et procédé

Country Status (1)

Country Link
WO (1) WO2017002885A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018116950A1 (fr) * 2016-12-20 2018-06-28 日本ペイントホールディングス株式会社 Film de revêtement composite, procédé de production d'un film de revêtement composite, article et composition de revêtement

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6420274A (en) * 1987-06-17 1989-01-24 Vianova Kunstharz Ag Water dilutive brush coating paint based on water-soluble alkyd resin
JPH02500450A (ja) * 1986-06-12 1990-02-15 ウイトコ・コーポレーション 金属のための被覆用腐食抑制組成物
JPH0299566A (ja) * 1988-10-06 1990-04-11 Kanto Auto Works Ltd 防錆剤組成物
JPH02170877A (ja) * 1988-12-23 1990-07-02 Matsushita Electric Works Ltd ケイ素アルコキシド系塗料の製造方法
JP2003138214A (ja) * 2001-10-30 2003-05-14 Asahipen Corp ジェル状ニス及びジェル状塗料
JP2008038123A (ja) * 2006-08-09 2008-02-21 Hyundai Motor Co Ltd 防錆ワックス組成物
CN101386770A (zh) * 2007-09-14 2009-03-18 中涂化工（上海）有限公司 一种高耐候性无铅催化剂醇酸树脂面漆
CN103937393A (zh) * 2014-05-06 2014-07-23 天津灯塔涂料工业发展有限公司 一种酚醛改性醇酸防锈涂料及其制备方法

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02500450A (ja) * 1986-06-12 1990-02-15 ウイトコ・コーポレーション 金属のための被覆用腐食抑制組成物
JPS6420274A (en) * 1987-06-17 1989-01-24 Vianova Kunstharz Ag Water dilutive brush coating paint based on water-soluble alkyd resin
JPH0299566A (ja) * 1988-10-06 1990-04-11 Kanto Auto Works Ltd 防錆剤組成物
JPH02170877A (ja) * 1988-12-23 1990-07-02 Matsushita Electric Works Ltd ケイ素アルコキシド系塗料の製造方法
JP2003138214A (ja) * 2001-10-30 2003-05-14 Asahipen Corp ジェル状ニス及びジェル状塗料
JP2008038123A (ja) * 2006-08-09 2008-02-21 Hyundai Motor Co Ltd 防錆ワックス組成物
CN101386770A (zh) * 2007-09-14 2009-03-18 中涂化工（上海）有限公司 一种高耐候性无铅催化剂醇酸树脂面漆
CN103937393A (zh) * 2014-05-06 2014-07-23 天津灯塔涂料工业发展有限公司 一种酚醛改性醇酸防锈涂料及其制备方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018116950A1 (fr) * 2016-12-20 2018-06-28 日本ペイントホールディングス株式会社 Film de revêtement composite, procédé de production d'un film de revêtement composite, article et composition de revêtement

Similar Documents

Publication Publication Date Title
CA2829861C (fr) Composition de revetement a base d'alkyde
ES2584064T3 (es) Agente secante para composiciones de revestimiento auto-oxidables
WO2011118526A1 (fr) Composition de revêtement antitache et son utilisation
CN103998545B (zh) 用于可自氧化的涂料组合物的干燥剂
JP6177983B1 (ja) 複層塗膜形成方法及び塗料組成物
TW201431988A (zh) 用於可自氧化之塗料組合物之乾燥劑
JP5921001B2 (ja) 塗装体
JPWO2021006290A1 (ja) 硬化性樹脂組成物、硬化膜、被覆樹脂成型体及び多層フィルム
JP7011556B2 (ja) 塗料組成物及び複層塗膜形成方法
JP5863936B1 (ja) エアゾール用塗料組成物とその塗膜を有する金属製機械部品
WO2017002885A1 (fr) Film de revêtement composite à couche de surface pelable, composition de revêtement pour former le film de revêtement composite et procédé
JP6746400B2 (ja) 表層剥離可能な複合塗膜、複合塗膜を形成するための塗料組成物および方法
CN1057316C (zh) 具有改进的基质粘着性的可固化组合物及其在涂覆基质方面的应用
CN106661230A (zh) 水分散性树枝状聚合物
CN111133068A (zh) 水性防锈涂料组合物、防锈涂膜、带有防锈涂膜的基材和带有防锈涂膜的基材的制造方法
JP2022151823A (ja) 低光沢塗料組成物
JP2008189894A (ja) アルキド系塗料組成物およびその製造方法
JP5608301B1 (ja) ２価金属含有樹脂の製造方法及び２価金属含有樹脂
JP7636866B2 (ja) 被膜形成方法
JP2024115299A (ja) 環境対応型アルキド樹脂塗料
JPS5867767A (ja) 防汚塗料
JPS6183263A (ja) 酸化乾燥型塗料
Kumar et al. Study on effects of micron and nano zinc oxide pigments on air drying property of alkyd paint
JP2023135579A (ja) 変性（メタ）アクリル樹脂系塗料組成物、積層塗膜、塗膜付き基材およびその製造方法
JP2024146708A (ja) 水系塗料組成物及び複層塗膜形成方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16817993

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: 2016817993

Country of ref document: EP