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WO2016067367A1 - Composition primaire et procede pour la fabrication d'article revêtu - Google Patents

Composition primaire et procede pour la fabrication d'article revêtu Download PDF

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Publication number
WO2016067367A1
WO2016067367A1 PCT/JP2014/078628 JP2014078628W WO2016067367A1 WO 2016067367 A1 WO2016067367 A1 WO 2016067367A1 JP 2014078628 W JP2014078628 W JP 2014078628W WO 2016067367 A1 WO2016067367 A1 WO 2016067367A1
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WO
WIPO (PCT)
Prior art keywords
equivalent
epoxy resin
primer composition
norbornene
curing agent
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/JP2014/078628
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English (en)
Japanese (ja)
Inventor
泰之 瀬戸
慎治 植山
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.)
Tohpe Corp
Original Assignee
Tohpe Corp
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 Tohpe Corp filed Critical Tohpe Corp
Priority to JP2015513930A priority Critical patent/JP5766898B1/ja
Priority to PCT/JP2014/078628 priority patent/WO2016067367A1/fr
Priority to KR1020157030529A priority patent/KR101629712B1/ko
Publication of WO2016067367A1 publication Critical patent/WO2016067367A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins

Definitions

  • the present invention relates to a primer composition and a method for producing a coated product. More specifically, the present invention relates to a primer composition used for coating a norbornene-based resin molded product, and a method for producing a coated product obtained by coating a norbornene-based resin molded product with a primer composition.
  • Patent Document 1 proposes a coating method using a two-component curable polyurethane surfacer.
  • Patent Document 2 proposes a coating method using an aqueous polyurethane resin paint.
  • the two-component curable polyurethane surfacer described in Patent Document 1 still cannot form a coating film exhibiting sufficient adhesion to norbornene-based resin molded products.
  • the two-component curable polyurethane surfacer described in Patent Document 1 forms a coating film exhibiting sufficient adhesion to a norbornene-based resin molded product that has been exposed to sunlight for 3 days or more immediately after molding. I can't.
  • the coating method of patent document 2 cannot form the coating film which shows sufficient adhesiveness depending on the shape of a resin molded product.
  • the coating method described in Patent Document 2 cannot use the coating equipment used in the conventional solvent-type paint in the case of the 2-coat 1-bake coating specification.
  • Patent Document 1 and Patent Document 2 conventionally, a technique for solving the problem by adjusting other components with polyurethane as a main component has been adopted. That is, in this technical field, it is common technical knowledge to use polyurethane, and in the first place, a coating film for a norbornene-based resin composition is formed using a component other than polyurethane (for example, epoxy resin as in the present invention) as a main component. Nothing is assumed.
  • a component other than polyurethane for example, epoxy resin as in the present invention
  • the present invention has been made in view of such conventional problems, and a coating film having sufficient adhesion without requiring special pretreatment such as polishing for norbornene-based resin molded products. It is an object of the present invention to provide a primer composition capable of forming
  • a primer composition containing an epoxy resin and an amine-based curing agent does not need to grind the surface of a norbornene-based resin molded product.
  • the present invention has been completed by finding that good adhesiveness can be obtained in a resin-based resin molded product. Furthermore, the present inventors have found that a primer composition with better adhesion can be obtained by further using a specific pigment in combination with an epoxy resin and an amine curing agent as a more preferred embodiment of the invention.
  • the primer composition of one aspect of the present invention that solves the above problems is a primer composition that contains an epoxy resin and an amine-based curing agent and is used for coating a norbornene-based resin molded product.
  • mode of this invention is a coated article including the coating process which coats the primer composition containing an epoxy resin and an amine type hardening
  • the primer composition of one embodiment of the present invention contains an epoxy resin and an amine curing agent.
  • the primer composition is used for coating a norbornene-based resin molded product.
  • Epoxy resin is an organic compound having at least one epoxy group. Epoxy resin is blended as a main component of the primer composition because it has adhesion to the surface of a norbornene-based resin molded product.
  • the number of epoxy groups in the epoxy resin may be one or more per molecule, and is preferably two or more. The number of epoxy groups per molecule is determined by dividing the total number of epoxy groups in the epoxy resin by the total number of molecules in the epoxy resin.
  • the epoxy resin is not particularly limited, and a conventionally known epoxy resin is used.
  • the epoxy resin is a bisphenol type epoxy resin, a novolac type epoxy resin, an aromatic epoxy resin, an alicyclic epoxy resin, an aliphatic epoxy resin, a glycidyl ester type epoxy resin, a glycidyl amine type epoxy resin, or the like.
  • Examples of the bisphenol type epoxy resin include a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol AD type epoxy resin, a bisphenol S type epoxy resin, and brominated products and water additives thereof.
  • Examples of novolak type epoxy resins include phenol novolak type epoxy resins and cresol novolak type epoxy resins.
  • Examples of the aromatic epoxy resin include trisphenol methane triglycidyl ether.
  • alicyclic epoxy resins include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-2-methylcyclohexylmethyl-3,4-epoxy-2-methylcyclohexanecarboxylate Bis (3,4-epoxycyclohexyl) adipate, bis (3,4-epoxycyclohexylmethyl adipate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 2- (3,4-epoxycyclohexyl-5 , 5-spiro-3,4-epoxycyclohexanone-meta-dioxane, bis (2,3-epoxycyclopentyl) ether, and the like.
  • Aliphatic epoxy resins include 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, and polyethylene glycol diglycidyl ether. Examples thereof include diglycidyl ether of polypropylene glycol, and polyglycidyl ether of long-chain polyols containing polyoxyalkylene glycol having 2 to 9 carbon atoms and polytetramethylene ether glycol.
  • glycidyl ester type epoxy resins include phthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, diglycidyl-p-oxybenzoic acid, salicylic acid glycidyl ether-glycidyl ester, dimer acid glycidyl ester Etc. are exemplified.
  • Examples of the glycidylamine type epoxy resin include triglycidyl isocyanurate, N, N′-diglycidyl derivative of cyclic alkylene urea, N, N, O-triglycidyl derivative of p-aminophenol, N, N, O of m-aminophenol. -Triglycidyl derivatives and the like are exemplified.
  • the epoxy resin is preferably a bisphenol type epoxy resin from the viewpoint that the formed coating film exhibits higher adhesion with a norbornene-based resin molded product, and is preferably a bisphenol A type epoxy resin or a bisphenol F type epoxy resin. Of these, at least one of them is more preferable.
  • These epoxy resins may be used independently and 2 or more types may be used together.
  • the epoxy resin equivalent of the epoxy resin is preferably 100 g / equivalent or more, more preferably 150 g / equivalent or more, and further preferably 180 g / equivalent or more. preferable.
  • the epoxy resin equivalent is preferably 2500 g / equivalent or less, more preferably 2200 g / equivalent or less, and still more preferably 2000 g / equivalent or less.
  • the epoxy resin equivalent is less than 100 g / equivalent, the molecular weight of the epoxy resin is lowered, so that the coating liquid viscosity tends to be lowered.
  • an epoxy resin equivalent exceeds 2500 g / equivalent, the viscosity of an epoxy resin becomes high and it tends to become difficult to attach a required coating film thickness.
  • the content of the resin solid content epoxy resin in the primer composition varies depending on the difference in the solid content of the paint, and thus is not generally determined.
  • the resin solid content in the primer composition is preferably 5 to 55% by weight.
  • the amine curing agent is blended to cure the above-described epoxy resin.
  • the amine curing agent is not particularly limited as long as it contains an amino group.
  • examples of the amine curing agent include a primary amino group-containing amine compound, a secondary amino group-containing amine compound, and a compound having both a tertiary amino group and an active hydrogen group.
  • the active hydrogen group is a functional group that can react with the epoxy group of the curing agent component.
  • the active hydrogen group is not particularly limited, and examples thereof include a primary amino group, a secondary amino group, a hydroxyl group, a thiol group, a carboxyl group, and a hydrazide group.
  • examples of the amine curing agent include a chain aliphatic amine, a cyclic aliphatic amine, and an aromatic amine.
  • chain aliphatic amines examples include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, polyoxypropylenediamine, polyoxypropylenetriamine, and derivatives thereof.
  • Cycloaliphatic amines include mensendiamine, isophoronediamine, bis (4-amino-3-methylcyclohexyl) methane, diaminodicyclohexylmethane, bis (aminomethylcyclohexane, N-aminoethylpiperazine, 3,9- Examples thereof include bis (3-aminopropyl) 2,4,8,10-tetraoxaspiro (5,5) undecane and derivatives thereof.
  • Aromatic amines include m-xylenediamine, ⁇ - (m / p aminophenyl) ethylamine, m-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, ⁇ , ⁇ -bis (4-aminophenyl-p-diisopropylbenzene, etc. And their derivatives.
  • the active hydrogen equivalent of the amine curing agent is preferably 50 g / equivalent or more, and 90 g / equivalent or more. Is more preferably 150 g / equivalent or more. Further, the active hydrogen equivalent of the amine curing agent is preferably 700 g / equivalent or less, more preferably 600 g / equivalent or less, and further preferably 500 g / equivalent or less. In addition, when the active hydrogen equivalent of the amine curing agent is less than 50 g / equivalent, the resin molecular weight of the amine curing agent is decreased, and the viscosity is decreased, so that it is difficult to provide a necessary film thickness.
  • the active hydrogen equivalent exceeds 700 g / equivalent
  • the molecular weight of the amine curing agent increases, so that the solid content of the coating liquid decreases, the required film thickness becomes difficult to attach, and the crosslinking density tends to decrease, And moisture resistance tend to decrease.
  • the active hydrogen in the amine curing agent is 0.35 equivalent or more with respect to 1 equivalent of the epoxy group contained in the epoxy resin from the viewpoint of interlayer adhesion with the top coat and coating workability. It is preferably 0.4 equivalents or more, more preferably 0.5 equivalents or more. Further, the active hydrogen in the amine curing agent with respect to 1 equivalent of the epoxy group contained in the epoxy resin is preferably 2.0 equivalents or less, more preferably 1.5 equivalents or less, and 1.0 equivalents or less. More preferably. When the active hydrogen equivalent of the amine curing agent is less than 0.35 equivalent, the reaction rate with the epoxy resin decreases, and the time until the top coat can be applied tends to be longer. On the other hand, when the active hydrogen equivalent of the amine curing agent exceeds 2.0 equivalents, the reaction rate with the epoxy resin increases, and the time for developing the solvent resistance tends to be shortened. Tend to decrease.
  • the primer composition of this embodiment is more favorable by using together a specific pigment (a talc, mica, clay, and also a specific pigment may be called hereafter) as shown in the modification 1 mentioned later. Adhesion can be obtained.
  • a specific pigment a talc, mica, clay, and also a specific pigment may be called hereafter
  • the above-mentioned epoxy resin and amine curing agent are appropriately dissolved in a solvent and used.
  • the solvent is not particularly limited.
  • the solvent is a hydrocarbon, a ketone, an ester, an alcohol, or the like.
  • hydrocarbons include benzene, toluene, xylene, cyclohexane, hexane, heptane, octane, mineral spirit, naphtha, and the like.
  • ketones include acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), and the like.
  • the esters include ethyl acetate, n-butyl acetate, propylene glycol monomethyl ether acetate and the like.
  • alcohols include methanol, ethanol, isopropanol, n-butanol, isobutanol, butyl cellosolve, butyl carbitol and the like.
  • the solvent is preferably an organic solvent. . By using the organic solvent, the adhesion between the norbornene-based resin molded product and the coating film is easily improved by the anchor effect.
  • These solvents may be used independently and 2 or more types may be used together.
  • the norbornene-based resin molded product can be obtained by polymerizing and molding a norbornene-based monomer.
  • Norbornene-based resins are resistant to low temperature impact, have high heat resistance, and are suitable for thick molding. Therefore, norbornene-based resins are widely used in housings such as water tanks, septic tanks, bathtubs, various exterior parts and interior parts of automobiles and construction machinery.
  • Conventional coatings are generally known to have a coating film that is difficult to apply to a norbornene-based resin molded product immediately after molding when the surface of the norbornene-based resin molded product is only subjected to degreasing treatment.
  • a coating film having sufficient adhesion cannot be formed on a norbornene-based resin molded product whose surface has deteriorated due to oxidation or the like due to exposure to sunlight for a long period of time. Therefore, the conventional paint is applied after a special pretreatment (for example, polishing) of the norbornene resin molded product.
  • polishing refers to an operation to increase the surface area by processing the surface of a norbornene-based resin molded product into a rough state.
  • the primer composition of this embodiment contains the above-described epoxy resin and amine curing agent.
  • the primer composition can form a coating film having sufficient adhesion without requiring special pretreatment such as polishing. Since the primer composition of the present embodiment does not require special pretreatment such as polishing, it is easily applied to a member processed into a curved shape or the like (for example, an automobile exterior part such as a bumper or a grill).
  • the primer composition of the present embodiment does not require special pretreatment such as polishing. However, the primer composition of this embodiment may be appropriately subjected to normal pretreatment (for example, deoiling treatment).
  • the norbornene-based monomer used for obtaining a norbornene-based resin molded product is a cycloolefin having a norbornene ring.
  • Examples of such monomers include dicyclopentadiene, dihydrodicyclopentadiene, tetracyclododecene, and tricyclopentadiene.
  • metathesis catalysts used in bulk polymerization include tungsten hexachloride, ammonium ammonium molybdate such as tridodecyl ammonium molybdate, tri (tridecyl ammonium) molybdate, and the like.
  • a known ruthenium carbene complex may be used as the metathesis catalyst.
  • Examples of the activator include alkylaluminum halides such as ethylaluminum dichloride and diethylaluminum chloride, alkoxyalkylaluminum halides obtained by substituting a part of alkyl groups of these alkylaluminum halides with alkoxy groups, and organotin compounds.
  • alkylaluminum halides such as ethylaluminum dichloride and diethylaluminum chloride
  • alkoxyalkylaluminum halides obtained by substituting a part of alkyl groups of these alkylaluminum halides with alkoxy groups
  • organotin compounds organotin compounds.
  • Bulk polymerization is performed, for example, by a method in which a liquid composed of a norbornene monomer and a metathesis catalyst and a liquid composed of a norbornene monomer and an activator are mixed and injected into a mold.
  • Primer composition containing specific pigment The primer composition of the present modification further includes a specific pigment, and the epoxy resin equivalent of the epoxy resin and the active hydrogen equivalent of the amine curing agent are in a predetermined range.
  • the primer composition of the present modification further includes a specific pigment, and the epoxy resin equivalent of the epoxy resin and the active hydrogen equivalent of the amine curing agent are in a predetermined range.
  • the specific pigment is a pigment having a major axis and a minor axis in a plan view and having an average particle diameter larger than the thickness.
  • the average particle diameter of the specific pigment refers to the average value of the long diameter and the short diameter when the plane of the specific pigment is viewed from the opposite direction. For example, 100 photographs are taken with a scanning electron microscope (SEM) of the specific pigment. This specific pigment can be determined by measuring the major axis and minor axis.
  • Specific pigments are limited to talc, clay and mica in so-called scaly pigments having an average particle diameter larger than the thickness. These specific pigments may be used alone or in combination. By using these specific pigments together, the resulting coating film exhibits better adhesion, water resistance and moisture resistance to norbornene-based resin molded products.
  • the pigment volume concentration of the specific pigment of the primer composition of Modification 1 may exceed 0%.
  • PVC the ratio (volume%) of the pigment occupying in the solid content of the paint
  • PVC the ratio (volume%) of the pigment occupying in the solid content of the paint
  • the primer composition of Modification 1 can be used in combination with the above-mentioned specific pigment and a pigment generally used in a paint such as a colored pigment.
  • a specific pigment and a colored pigment are used in combination with an epoxy resin and an amine curing agent
  • the combined pigment volume concentration of the specific pigment and the colored pigment is preferably more than 0%, 4% or more (specific pigment 2%, 2%), more preferably 8% or more (4% specific pigment, 4% color pigment, etc.).
  • the pigment volume concentration of the specific pigment and the color pigment combined is preferably 50% or less, more preferably 45% or less, and further preferably 40% or less.
  • the pigment volume concentration combining the specific pigment of the primer composition and the colored pigment exceeds 50%, the surface area of the pigment is increased, so that it is difficult to form a coating film. It tends to settle and tends to make it difficult to form a uniform coating film.
  • the epoxy resin equivalent of the epoxy resin is preferably 100 g / equivalent or more, more preferably 150 g / equivalent or more, and 180 g / equivalent or more. More preferably.
  • the epoxy resin equivalent is preferably 2500 g / equivalent or less, more preferably 2200 g / equivalent or less, and still more preferably 2000 g / equivalent or less.
  • the epoxy resin equivalent is less than 100 g / equivalent, the molecular weight of the epoxy resin is lowered, so that the coating liquid viscosity tends to be lowered.
  • an epoxy resin equivalent exceeds 2500 g / equivalent, the viscosity of an epoxy resin becomes high and it tends to become difficult to attach a required coating film thickness.
  • the active hydrogen equivalent of the amine-based curing agent is preferably 50 g / equivalent or more, and 90 g / equivalent or more. More preferably, it is more preferably 150 g / equivalent or more. Further, the active hydrogen equivalent of the amine curing agent is preferably 700 g / equivalent or less, more preferably 600 g / equivalent or less, and further preferably 500 g / equivalent or less.
  • the active hydrogen equivalent of the amine curing agent when the active hydrogen equivalent of the amine curing agent is less than 50 g / equivalent, the resin molecular weight of the amine curing agent is decreased, and the viscosity is decreased, so that it is difficult to provide a necessary film thickness.
  • the active hydrogen equivalent exceeds 700 g / equivalent, the molecular weight of the amine-based curing agent is increased, so that the solid content of the coating liquid is reduced, so that the required film thickness is difficult to attach and the crosslinking density tends to decrease, Water resistance and moisture resistance tend to decrease.
  • the active hydrogen in the amine-based curing agent with respect to 1 equivalent of the epoxy group contained in the epoxy resin is preferably 0.35 equivalent or more, and more preferably 0.4 equivalent or more. More preferably, it is 0.5 equivalent or more. Further, the active hydrogen in the amine curing agent with respect to 1 equivalent of the epoxy group contained in the epoxy resin is preferably 2.0 equivalents or less, more preferably 1.5 equivalents or less, and 1.0 equivalents or less. More preferably.
  • the active hydrogen equivalent of the amine curing agent is less than 0.35 equivalent, the reaction rate with the epoxy resin decreases, and the time until the top coat can be applied tends to be longer.
  • the active hydrogen equivalent of the amine curing agent exceeds 2.0 equivalents, the reaction rate with the epoxy resin increases, and the time for developing the solvent resistance tends to be shortened. Tend to decrease.
  • an epoxy resin having a relatively wide range of epoxy resin equivalents as described above or an amine curing agent having an active hydrogen equivalent is used.
  • a coating film with good adhesion can be formed on the surface of the norbornene-based resin molded product without requiring special pretreatment such as polishing.
  • ⁇ Modification 2 Primer composition showing specific epoxy resin equivalent and active hydrogen equivalent>
  • the epoxy resin equivalent of the epoxy resin and the active hydrogen equivalent of the amine curing agent are in a predetermined range.
  • the description which overlaps with above-described embodiment is abbreviate
  • the epoxy resin equivalent of the epoxy resin is preferably 100 g / equivalent or more, more preferably 150 g / equivalent or more, and 180 g / equivalent or more. More preferably.
  • the epoxy resin equivalent is preferably 2500 g / equivalent or less, more preferably 2200 g / equivalent or less, and still more preferably 2000 g / equivalent or less.
  • the epoxy resin equivalent is less than 100 g / equivalent, the molecular weight of the epoxy resin is lowered, so that the coating liquid viscosity tends to be lowered.
  • an epoxy resin equivalent exceeds 2500 g / equivalent, the viscosity of an epoxy resin becomes high and it tends to become difficult to attach a required coating film thickness.
  • the active hydrogen equivalent of the amine-based curing agent is preferably 50 g / equivalent or more, and 90 g / equivalent or more. More preferably, it is more preferably 150 g / equivalent or more. Further, the active hydrogen equivalent of the amine curing agent is preferably 700 g / equivalent or less, more preferably 600 g / equivalent or less, and further preferably 500 g / equivalent or less.
  • the active hydrogen equivalent of the amine curing agent when the active hydrogen equivalent of the amine curing agent is less than 50 g / equivalent, the resin molecular weight of the amine curing agent is decreased, and the viscosity is decreased, so that it is difficult to provide a necessary film thickness.
  • the active hydrogen equivalent exceeds 700 g / equivalent, the molecular weight of the amine curing agent increases, so that the solid content of the coating liquid decreases, the required film thickness becomes difficult to attach, and the crosslinking density tends to decrease, And moisture resistance tend to decrease.
  • the active hydrogen in the amine-based curing agent with respect to 1 equivalent of the epoxy group contained in the epoxy resin is preferably 0.35 equivalent or more, and more preferably 0.4 equivalent or more. More preferably, it is 0.5 equivalent or more. Further, the active hydrogen in the amine curing agent with respect to 1 equivalent of the epoxy group contained in the epoxy resin is preferably 2.0 equivalents or less, more preferably 1.5 equivalents or less, and 1.0 equivalents or less. More preferably.
  • the active hydrogen equivalent of the amine curing agent is less than 0.35 equivalent, the reaction rate with the epoxy resin decreases, and the time until the top coat can be applied tends to be longer.
  • the active hydrogen equivalent of the amine curing agent exceeds 2.0 equivalents, the reaction rate with the epoxy resin increases, and the time for developing the solvent resistance tends to be shortened. Tend to decrease.
  • the specific pigment as in Modification 1 can be obtained by using an epoxy resin having an epoxy resin equivalent in a predetermined range as described above or an amine curing agent having an active hydrogen equivalent. Even if it does not contain, a coating film with good adhesion can be formed on the surface of a norbornene-based resin molded product that has not been subjected to special pretreatment such as polishing.
  • the primer composition of the present embodiment may appropriately contain other components in addition to the above-described epoxy resin and amine curing agent.
  • other components include inorganic fillers (excluding the specific pigment described above), flame retardants, leveling agents, antifoaming agents, coupling agents, and the like.
  • inorganic fillers examples include silicates such as glass, titanium oxide, alumina, fused silica (fused spherical silica, fused crushed silica), oxides such as silica powder such as synthetic silica and crystalline silica, calcium carbonate, magnesium carbonate, Carbonates such as hydrotalcite, hydroxides such as aluminum hydroxide, magnesium hydroxide, calcium hydroxide, sulfates or sulfites such as barium sulfate, calcium sulfate, calcium sulfite, zinc borate, barium metaborate, boron
  • examples thereof include borates such as aluminum oxide, calcium borate, and sodium borate, and nitrides such as aluminum nitride, boron nitride, and silicon nitride.
  • Flame retardants include halogenated flame retardants such as brominated epoxy resins and brominated phenolic resins, antimony compounds such as antimony trioxide, phosphorus flame retardants such as red phosphorus, phosphate esters, phosphines, melamine derivatives, etc.
  • halogenated flame retardants such as brominated epoxy resins and brominated phenolic resins
  • antimony compounds such as antimony trioxide
  • phosphorus flame retardants such as red phosphorus, phosphate esters, phosphines, melamine derivatives, etc.
  • Illustrative examples include nitrogen-based flame retardants and inorganic flame retardants such as aluminum hydroxide and magnesium hydroxide.
  • Leveling agents include acrylates such as ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate and the like, oligomers having a molecular weight of 4000 to 12000, epoxidized soybean fatty acid, epoxidized abiethyl alcohol, hydrogenated castor oil, titanium-based coupling agents, etc. Is exemplified.
  • antifoaming agent examples include isoparaffin, liquid paraffin, silicon oil, polysiloxane oligomers, fluorine compounds, copolymers of acrylic acid esters and vinyl compounds, and the like.
  • Examples of coupling agents include silane coupling agents and titanate coupling agents.
  • the primer composition of this embodiment contains the above-described epoxy resin and an amine curing agent.
  • the adhesion between the formed coating film and the surface of the norbornene resin molded product is excellent.
  • an epoxy resin and an amine curing agent By including an epoxy resin and an amine curing agent, a part of the epoxy resin penetrates and adheres to the surface of the norbornene resin molded product.
  • Such a primer composition of the present embodiment can be applied to a norbornene-based resin molded product by simply performing a degreasing treatment as appropriate without requiring special pretreatment such as polishing.
  • the manufacturing method of the coated product of this embodiment includes the coating process which coats the primer composition containing an epoxy resin and an amine hardening
  • a known process for example, a drying process
  • the painting process is a process of coating the primer composition on a norbornene-based resin molded product.
  • a degreasing process for degreasing the surface of the norbornene resin molded product may be employed as appropriate.
  • the primer composition can form a coating film having high adhesion even to norbornene-based resin molded products exposed to sunlight outdoors for 3 days or more immediately after molding or after molding. Therefore, the primer composition can be applied to, for example, an automobile exterior part processed into a curved shape or the like without requiring a special pretreatment such as polishing.
  • the primer composition can be applied without polishing the surface of the norbornene-based resin composition.
  • the surface of the norbornene-based resin composition may be appropriately polished before the primer composition is applied. Thereby, a primer composition and the surface of a norbornene-type resin composition show the further favorable adhesiveness, and the coating film obtained can show the further favorable water resistance and moisture resistance.
  • a conventionally known coating method can be used as the primer composition coating method.
  • the primer composition is heated as necessary, adjusted to a desired viscosity by adding an organic solvent such as thinner, and then air spray, airless spray, electrostatic air spray, flow coater, dipping type, etc.
  • the coating can be performed using a commonly used coating machine such as a coating machine or a brush. Among these coating methods, air spray coating is preferable.
  • the dry film thickness of the resulting coating film (primer coating film) is preferably 2 ⁇ m or more, more preferably 5 ⁇ m or more, and even more preferably 10 ⁇ m or more.
  • the dry film thickness is preferably 70 ⁇ m or less, more preferably 50 ⁇ m or less, and further preferably 30 ⁇ m or less.
  • the primer coating may be allowed to stand (setting) to stabilize the coating before the drying step.
  • the coating film that has undergone the coating process may be appropriately dried, repaired with a second coat of top coat, putty, primer surfacer, top coat, and the like.
  • the drying process is a process for forcibly drying the primer coating. Drying conditions are not particularly limited. Drying is performed, for example, by leaving the coating film at room temperature and then drying it at a temperature of 20 to 100 ° C. for 5 to 60 minutes.
  • the primer surfacer can be applied by a conventionally known coating method. Drying after coating is performed, for example, by leaving the coating film at room temperature and then drying it at a temperature of 20 to 100 ° C. for 5 to 60 minutes.
  • the top coat paint applied to the primer composition is applied using a paint containing a colored pigment, or a paint containing a colored pigment is applied, and then a clear paint is applied, etc. . These coating methods are appropriately selected depending on the required color and texture.
  • top coat The paint used for the top coat (top coat) may be applied wet-on-wet without baking after applying the primer composition.
  • top coat urethane paint, fluorine paint, or the like is appropriately used.
  • a primer composition that can sufficiently adhere to a norbornene-based resin molded product is coated on the surface of the norbornene-based resin molded product without requiring polishing. Therefore, according to such a method for producing a coated product, it is possible to produce a coated product on which a coating film having sufficient adhesion is formed at low cost.
  • a primer composition containing an epoxy resin and an amine curing agent and used for coating a norbornene resin molded product (1) A primer composition containing an epoxy resin and an amine curing agent and used for coating a norbornene resin molded product.
  • the primer composition does not require a special pretreatment such as polishing, and even when applied to a norbornene-based resin molded product, the primer composition has a sufficient adhesion. Can be formed.
  • a specific pigment is further contained, the epoxy resin equivalent of the epoxy resin is 100 to 2500 g / equivalent, and the active hydrogen equivalent of the amine-based curing agent is 50 to 700 g / equivalent.
  • the active hydrogen in the amine-based curing agent with respect to 1 equivalent of the epoxy group contained is 0.35 to 2.0 equivalent, and in the dry coating film obtained by coating the primer composition on the norbornene-based resin molded product.
  • the epoxy resin has an epoxy resin equivalent of 100 to 2500 g / equivalent, and the amine-based curing agent has an active hydrogen equivalent of 50 to 700 g / equivalent to 1 equivalent of epoxy group contained in the epoxy resin.
  • the formed coating film exhibits higher adhesion with the norbornene-based resin molded product.
  • the surface of a resin molded product having a curved shape such as a car exterior part such as a bumper or a grill, a car interior part, or a housing of a resin home appliance is difficult to polish.
  • the primer composition of the present invention does not require special treatment such as polishing. Therefore, it can be applied to such molded products.
  • the obtained coating film is difficult to peel off from the resin molded product having these curved portions.
  • a method for producing a coated product comprising a coating step of coating a primer composition containing an epoxy resin and an amine curing agent on the surface of the norbornene resin molded product.
  • the primer composition is coated on the surface of the norbornene-based resin molded product. Even when the primer composition is applied to a norbornene-based resin molded product, a coating film having sufficient adhesion can be formed. Therefore, according to such a method for producing a coated product, a coated product on which a coating film having good adhesion, moisture resistance, and water resistance is formed can be produced.
  • the primer composition and the surface of the norbornene-based resin composition exhibit better adhesion, and the obtained coating film can exhibit better water resistance and moisture resistance.
  • the adhesion of the coating film decreases. Therefore, when applying a conventional paint, pretreatment such as polishing is performed on the surface of the norbornene-based resin molded product.
  • pretreatment such as polishing is performed on the surface of the norbornene-based resin molded product.
  • the method for producing a coated product according to the present invention provides sufficient adhesion even for norbornene-based resin molded products whose surfaces are sufficiently oxidized by being exposed to sunlight outdoors for 3 days or more after molding.
  • the coating film which has can be formed. Therefore, it is not essential to perform a pretreatment such as polishing, and the coating can be performed, thereby reducing the manufacturing cost.
  • Epoxy resin A Epomic R-139 (solid content 100%, specific gravity 1.16, epoxy equivalent 185 g / equivalent, Mitsui Chemicals, Inc.)
  • Epoxy resin B DER671-X70 (solid content 70%, solid content specific gravity 1.19, epoxy equivalent 476 g / equivalent of solid content 100%, The Dow Chemical Company)
  • Epoxy resin C jER1004 (solid content 100%, specific gravity 1.19, epoxy equivalent 925 g / equivalent Mitsubishi Chemical Corporation)
  • Epoxy resin D jER4005P (solid content 100%, specific gravity 1.19, epoxy equivalent 1075 g / equivalent Mitsubishi Chemical Corporation)
  • Epoxy resin E jER1007 (solid content: 100%, specific gravity: 1.19, epoxy equivalent: 1975 g / equivalent Mitsubishi Chemical Corporation)
  • Acrylic polyol Acrydic A-827 (solid content 65%, solid content specific gravity 1.12, hydroxyl value 69 mg ⁇ KOH / mg in terms of solid content,
  • Polyamine-based curing agent A Tomide 245-HS (solid content 100%, specific gravity 0.95, active hydrogen equivalent 90 g / equivalent, T & K TOKA)
  • Polyamine curing agent B Tomide TXS-690 (solid content 55%, solid content specific gravity 1.05, active hydrogen equivalent 160 g / equivalent of solid content 100%, T & K TOKA Co., Ltd.)
  • Polyamine-based curing agent C Newmide 630 (solid content 60%, solid content specific gravity 1.06, active hydrogen equivalent 250 g / equivalent of solid content 100%, Harima Chemical Co., Ltd.)
  • Polyamine curing agent D VERSAMID JP1020 (solid content 65%, solid content specific gravity 1.19, active hydrogen equivalent 475 g / equivalent of solid content 100%, BASF)
  • Isocyanate-based curing agent Coronate HX (solid content 100%, specific gravity 1.16, NCO content 21%, Nippon Polyurethane Industry Co., Ltd.)
  • Titanium oxide Titanium oxide FR-48 (specific gravity 4.20, Furukawa Chemicals)
  • Talc A Hytron A (specific pigment specific gravity 2.65, Takehara Chemical Industry Co., Ltd.)
  • Talc B Talc PK-50 (specific pigment specific gravity 2.80, Fuji Talc Industry Co., Ltd.)
  • Talc C Talc NK-48 (specific pigment specific gravity 2.80, Fuji Talc Industry Co., Ltd.)
  • Clay A Kaolin clay ASP-200 (specific pigment specific gravity 2.58, BASF)
  • Clay B HA Kaolin (specific pigment specific gravity 2.70, Sanyo Clay Industry Co., Ltd.)
  • Precipitated barium sulfate Precipitable barium sulfate (Fuhei) (specific gravity 4.30, Kawazu Sangyo Co., Ltd.)
  • Calcium carbonate Neolite SP-100 (specific gravity 2.65, Takehara Chemical Industry Co., Ltd
  • Additive A Leveling agent (Disparon 230; manufactured by Enomoto Kasei Co., Ltd.)
  • Additive B Dispersant, antifoaming agent (DISPERBYK-166; BYK, BYK-310; BYK, Disparon OX-750; manufactured by Enomoto Kasei Co., Ltd.)
  • Thinner A for dilution xylene 30 wt%, butanol 30 wt%, butyl cellosolve 40 wt%
  • Examples 1 to 39, Comparative Examples 1 to 5> (Preparation of primer composition (excluding curing agent)) According to the formulations shown in Tables 1 to 3 below, the primer compositions of Examples 1 to 39 and Comparative Examples 1 to 5 (but not containing a curing agent) were prepared. Preparation of the primer composition was carried out by putting each component excluding the curing agent into a container and stirring and mixing with a sand mill dispersion and a disper.
  • the norbornene-based resin molded plate was stored in an aluminum lami zip (a bag in which aluminum was laminated with PET) immediately after reaction injection molding, purged with nitrogen, and protected from light in order to prevent surface ultraviolet rays and oxidative degradation. .
  • primer composition of the first coat was measured with an Iwata cup using a thinner for dilution by mixing the above-mentioned primer composition (excluding the curing agent) with each curing agent in Tables 1 to 3. The viscosity was adjusted so as to be 10 to 60 seconds.
  • top coat of the second coat is the time measured in the Iwata cup with the dilution thinner by mixing the above-mentioned primer composition (excluding the curing agent) with the isocyanate curing agent shown in Tables 1-3. The viscosity was adjusted so as to be 10 to 60 seconds.
  • ⁇ Moisture resistance test> Each test plate was tested for 240 hours in accordance with JIS K5600-7-2 moisture resistance conditions. Thereafter, 100 squares of 2 mm ⁇ 2 mm were prepared in accordance with JIS K5600-5.6 cross-cut method, and a cross-cut peel test was performed. The same standard as the primary adhesion test was adopted as the evaluation standard.
  • the primer compositions of Examples 1 to 11 using an epoxy resin and a polyamine curing agent showed good primary adhesion to a molded plate that is a norbornene resin molded product, In addition, water resistance and moisture resistance were also good.
  • the primer compositions of Examples 5 to 7 using an epoxy resin having an epoxy resin equivalent of 450 g / equivalent to 1100 g / equivalent were further excellent in water resistance and moisture resistance.
  • the primer compositions of Examples 12 to 26, 38 and 39 further containing a specific pigment showed good primary adhesion to a molded plate which is a norbornene resin molded product, and Water resistance and moisture resistance were also good.
  • the primer compositions of Examples 29 to 37 which further contain a specific pigment, showed good primary adhesion to a molded plate that is a norbornene-based resin molded product, and also had water resistance and moisture resistance. The property was also good. Among them, the primer compositions of Examples 30 to 37 having a high PVC exhibited even better water resistance and moisture resistance.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)

Abstract

La présente invention concerne une composition primaire comportant une résine époxy et un agent de durcissement à base d'amine et utilisée pour le revêtement d'un article moulé de résine à base de norbornène. Le procédé pour la fabrication d'un article revêtu comprend une étape de revêtement pour le revêtement d'une composition primaire comportant une résine époxy et un agent de durcissement à base d'amine sur un article moulé de résine à base de norbornène.
PCT/JP2014/078628 2014-10-28 2014-10-28 Composition primaire et procede pour la fabrication d'article revêtu Ceased WO2016067367A1 (fr)

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JP2015513930A JP5766898B1 (ja) 2014-10-28 2014-10-28 プライマー組成物および塗装品の製造方法
PCT/JP2014/078628 WO2016067367A1 (fr) 2014-10-28 2014-10-28 Composition primaire et procede pour la fabrication d'article revêtu
KR1020157030529A KR101629712B1 (ko) 2014-10-28 2014-10-28 프라이머 조성물 및 도장품의 제조방법

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JP2021134360A (ja) * 2020-02-26 2021-09-13 保土谷化学工業株式会社 ブリード防止プライマー、ブリード防止プライマーを用いたブリード防止構造及びその防止工法
WO2023203829A1 (fr) * 2022-04-22 2023-10-26 日本ペイント・インダストリアルコーティングス株式会社 Procédé de fabrication d'un film de revêtement à double couche

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KR101629712B1 (ko) * 2014-10-28 2016-06-13 가부시키가이샤 도우페 프라이머 조성물 및 도장품의 제조방법

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JPH083510A (ja) * 1994-06-20 1996-01-09 Nippon Zeon Co Ltd 新規なコート剤、およびコート層を有する成形品
JP2000300450A (ja) * 1999-04-26 2000-10-31 Nippon Zeon Co Ltd 洗面ボールおよびその製造方法
JP2003073631A (ja) * 2001-09-06 2003-03-12 Emulsion Technology Co Ltd ノルボルネン系樹脂基材の接着方法
JP2004035774A (ja) * 2002-07-04 2004-02-05 Mitsubishi Chemicals Corp プライマー用樹脂及びプライマー組成物及びそれからなる積層体
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2021134360A (ja) * 2020-02-26 2021-09-13 保土谷化学工業株式会社 ブリード防止プライマー、ブリード防止プライマーを用いたブリード防止構造及びその防止工法
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WO2023203829A1 (fr) * 2022-04-22 2023-10-26 日本ペイント・インダストリアルコーティングス株式会社 Procédé de fabrication d'un film de revêtement à double couche

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