WO2016067367A1 - プライマー組成物および塗装品の製造方法 - Google Patents
プライマー組成物および塗装品の製造方法 Download PDFInfo
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- 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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- epoxy resin
- primer composition
- norbornene
- curing agent
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- 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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Abstract
Description
以下、本発明の一実施形態のプライマー組成物について、詳細に説明する。本実施形態のプライマー組成物は、エポキシ樹脂と、アミン系硬化剤とを含む。プライマー組成物は、ノルボルネン系樹脂成型品の塗装に使用される。
エポキシ樹脂は、少なくとも1個のエポキシ基を有する有機化合物である。エポキシ樹脂は、ノルボルネン系樹脂成型品の表面と密着性を有するため、プライマー組成物の主たる成分として配合される。エポキシ樹脂中のエポキシ基の数は、1分子当たり1個以上であればよく、2個以上であることが好ましい。1分子当たりのエポキシ基の数は、エポキシ樹脂中のエポキシ基の総数をエポキシ樹脂中の分子の総数で除算することにより求められる。
アミン系硬化剤は、上記したエポキシ樹脂を硬化させるために配合される。アミン系硬化剤は、アミノ基を含有していれば特に限定されない。具体的には、アミン系硬化剤は、1級アミノ基含有アミン化合物、2級アミノ基含有アミン化合物および3級アミノ基と活性水素基とを併せ持つ化合物等が挙げられる。活性水素基は、硬化剤成分のエポキシ基と反応しうる官能基である。活性水素基は特に限定されず、1級アミノ基、2級アミノ基、水酸基、チオール基、カルボキシル基、ヒドラジド基等が例示される。
ノルボルネン系樹脂成型品は、ノルボルネン系モノマーを重合し、成型することにより得られる。ノルボルネン系樹脂は、低温衝撃に強く、高い耐熱性を有しており、かつ厚肉成型に適している。そのため、ノルボルネン系樹脂は、水槽や浄化槽、バスタブなどの筐体、自動車や建農機の各種外装部品、内装部品等に広く利用されている。
本変形例のプライマー組成物は、特定顔料をさらに含み、エポキシ樹脂のエポキシ樹脂当量およびアミン系硬化剤の活性水素当量が所定の範囲である。以下、それぞれについて説明する。なお、上記した実施形態と重複する説明は、適宜省略される。
特定顔料は、平面視において長径と短径とを有し、平均粒子径が厚みよりも大きい顔料である。特定顔料の平均粒子径は、特定顔料の平面を対向する方向から見た場合の長径と短径の平均値をいい、たとえば特定顔料の走査型電子顕微鏡(SEM)で写真を撮影し、100個の特定顔料について長径と短径とを測定することによって求めることができる。
本変形例において、密着性、耐水性、耐湿性の観点から、エポキシ樹脂のエポキシ樹脂当量は、100g/当量以上であることが好ましく、150g/当量以上であることがより好ましく、180g/当量以上であることがさらに好ましい。また、エポキシ樹脂当量は、2500g/当量以下であることが好ましく、2200g/当量以下であることがより好ましく、2000g/当量以下であることがさらに好ましい。エポキシ樹脂当量が、100g/当量未満の場合、エポキシ樹脂の分子量が低下するため、塗装液粘性が低下する傾向がある。一方、エポキシ樹脂当量が2500g/当量を超える場合、エポキシ樹脂の粘性が高くなり、必要な塗装膜厚を付けにくくなる傾向がある。
本変形例において、密着性、耐水性、耐湿性および必要な膜厚を1回の塗装で付ける観点から、アミン系硬化剤の活性水素当量は、50g/当量以上が好ましく、90g/当量以上であることがより好ましく、150g/当量以上であることがさらに好ましい。また、アミン系硬化剤の活性水素当量は、700g/当量以下であることが好ましく、600g/当量以下であることがより好ましく、500g/当量以下あることがさらに好ましい。また、アミン系硬化剤の活性水素当量が50g/当量未満の場合、アミン系硬化剤の樹脂分子量が低下するため、粘性が低下することから、必要な膜厚を付け難い傾向となる。また、活性水素当量が700g/当量を超える場合、アミン系硬化剤の分子量が高くなるため、塗装液固形分が低下するため、必要膜厚が付け難くなるとともに、架橋密度が低下する傾向となり、耐水性、耐湿性が低下する傾向となる。
本変形例のプライマー組成物は、エポキシ樹脂のエポキシ樹脂当量およびアミン系硬化剤の活性水素当量が所定の範囲である。以下、それぞれについて説明する。なお、上記した実施形態と重複する説明は、適宜省略される。
本変形例において、密着性、耐水性、耐湿性の観点から、エポキシ樹脂のエポキシ樹脂当量は、100g/当量以上であることが好ましく、150g/当量以上であることがより好ましく、180g/当量以上であることがさらに好ましい。また、エポキシ樹脂当量は、2500g/当量以下であることが好ましく、2200g/当量以下であることがより好ましく、2000g/当量以下であることがさらに好ましい。エポキシ樹脂当量が、100g/当量未満の場合、エポキシ樹脂の分子量が低下するため、塗装液粘性が低下する傾向がある。一方、エポキシ樹脂当量が2500g/当量を超える場合、エポキシ樹脂の粘性が高くなり、必要な塗装膜厚を付けにくくなる傾向がある。
本変形例において、密着性、耐水性、耐湿性および必要な膜厚を1回の塗装で付ける観点から、アミン系硬化剤の活性水素当量は、50g/当量以上が好ましく、90g/当量以上であることがより好ましく、150g/当量以上であることがさらに好ましい。また、アミン系硬化剤の活性水素当量は、700g/当量以下であることが好ましく、600g/当量以下であることがより好ましく、500g/当量以下であることがさらに好ましい。また、アミン系硬化剤の活性水素当量が50g/当量未満の場合、アミン系硬化剤の樹脂分子量が低下するため、粘性が低下することから、必要な膜厚を付け難い傾向となる。また、活性水素当量が700g/当量を超える場合、アミン系硬化剤の分子量が高くなるため、塗装液固形分が低下し、必要膜厚が付け難くなるとともに、架橋密度が低下する傾向となり、耐水性、耐湿性が低下する傾向となる。
本実施形態のプライマー組成物の説明に戻り、本実施形態のプライマー組成物は、上記したエポキシ樹脂およびアミン系硬化剤以外に、その他の成分を適宜含んでもよい。その他の成分としては、無機充填材(ただし上記した特定顔料を除く)、難燃剤、レベリング剤、消泡剤、カップリング剤等が例示される。
以下、本発明の一実施形態の塗装品の製造方法について、詳細に説明する。本実施形態の塗装品の製造方法は、エポキシ樹脂とアミン系硬化剤とを含有するプライマー組成物を、ノルボルネン系樹脂成型品に対して塗装する塗装工程を含む。なお、プライマー組成物は、上記した実施形態において詳述したものと同じであるため、重複する説明は適宜省略する。また、本実施形態の塗装品の製造方法は、塗装工程に特徴を有している。そのため、塗装工程以外の工程は、周知の工程であり、適宜変更することができる。また、目的とする塗膜の構成によって、塗装工程以外の工程は適宜選択される。たとえば、1コートの塗膜を形成する場合や、2コート以上の塗膜を形成する場合には、それぞれに必要な周知の工程(たとえば乾燥工程)および工程の回数、順序等が適宜選択される。
塗装工程は、プライマー組成物を、ノルボルネン系樹脂成型品に対して塗装する工程である。なお、この塗装工程では、ノルボルネン樹脂成型品の表面を脱脂処理する脱脂処理工程が適宜採用されてもよい。
塗装工程を経た塗膜に対し、適宜、乾燥、2コート目の上塗り塗装、パテ、プライマーサフェーサ、上塗り塗料を用いた補修塗装等が行われてもよい。
[プライマー成分(1コート目)]
<樹脂>
エポキシ樹脂A:エポミックR-139 (固形分100%、比重1.16、エポキシ当量185g/当量、三井化学(株))
エポキシ樹脂B:DER671-X70(固形分70%、固形分比重1.19、固形分100%換算のエポキシ当量476g/当量、The Dow Chemical Company社)
エポキシ樹脂C:jER1004(固形分100%、比重1.19、エポキシ当量 925g/当量 三菱化学(株))
エポキシ樹脂D:jER4005P(固形分100%、比重1.19、エポキシ当量 1075g/当量 三菱化学(株))
エポキシ樹脂E:jER1007(固形分100%、比重1.19、エポキシ当量 1975g/当量 三菱化学(株))
アクリルポリオール:アクリディックA-827(固形分65%、固形分比重1.12、固形分換算の水酸基価69mg・KOH/mg、DIC(株))
なお、以下の実施例では、上記エポキシ樹脂A、Bおよびアクリルポリオールはそのまま使用し、エポキシ樹脂CはjER1004 60wt%、IPA 2wt%、MIBK 13wt%、トルエン 25wt%を混合して調整したもの(固形分60%)を使用し、エポキシ樹脂DはjER4005P 60wt%、IPA 2wt%、MIBK 13wt%、トルエン 25wt%を混合して調整したもの(固形分60%)使用し、エポキシ樹脂EはjER1007 60wt%部、IPA 2wt%、MIBK 13wt%、トルエン 25wt%を混合して調整したもの(固形分60%)を使用した。
ポリアミン系硬化剤A:トーマイド 245-HS(固形分100%、比重 0.95、活性水素当量90g/当量、(株)T&K TOKA)
ポリアミン系硬化剤B:トーマイド TXS-690(固形分55%、固形分比重1.05、固形分100%換算の活性水素当量160g/当量、(株)T&K TOKA)
ポリアミン系硬化剤C:ニューマイド 630(固形分60%、固形分比重1.06、固形分100%換算の活性水素当量250g/当量、ハリマ化成(株))
ポリアミン系硬化剤D:VERSAMID JP1020(固形分65%、固形分比重1.19、固形分100%換算の活性水素当量475g/当量、BASF社)
イソシアネート系硬化剤:コロネートHX(固形分100%、比重1.16、NCO含有量21%、日本ポリウレタン工業(株))
酸化チタン:酸化チタンFR-48(比重4.20、古河ケミカルズ(株))
タルクA:ハイトロンA(特定顔料 比重2.65、竹原化学工業(株))
タルクB:タルクPK-50(特定顔料 比重2.80、富士タルク工業(株))
タルクC:タルクNK-48(特定顔料 比重2.80、富士タルク工業(株))
クレーA:カオリンクレーASP-200(特定顔料 比重2.58、BASF社)
クレーB:HAカオリン(特定顔料 比重2.70、山陽クレー工業(株))
マイカA:Iriodin 111Rutile Fine Satin(特定顔料 比重3.10、メルク(株))
沈降性硫酸バリウム:沈降性硫酸バリウム(フヘイ)(比重4.30、川津産業(株))
炭酸カルシウム:ネオライトSP-100(比重2.65、竹原化学工業(株))
添加剤A:レベリング剤(ディスパロン230;楠本化成(株)製)
添加剤B:分散剤、消泡剤(DISPERBYK-166;BYK社、BYK-310;BYK社、ディスパロンOX-750;楠本化成(株)製)
希釈用シンナーA:キシレン 30wt%、ブタノール 30wt%、ブチルセロソルブ 40wt%
希釈用シンナーB:トルエン 20wt%、キシレン 45wt%、酢酸エチル 5wt%、酢酸ブチル 14wt%、MIBK 10wt%、ソルベントPMアセテート 6wt%
(a)主剤:ネオウレタンA(主剤) 100重量部
(b)硬化剤:トアウレタンB(硬化剤) 20重量部
(c)希釈剤;トアリファイン2Kシンナー 30重量部
*いずれも(株)トウペ製
(プライマー組成物(硬化剤を除く)の調製)
以下の表1~3に記載の配合にしたがって、実施例1~39および比較例1~5のそれぞれのプライマー組成物(ただし硬化剤未配合)を調製した。プライマー組成物の調製は、硬化剤を除くそれぞれの成分を容器に入れ、サンドミル分散およびディスパーにて攪拌混合することにより行った。
ノルボルネン系樹脂成型板は、表面の紫外線および酸化劣化を防ぐために、反応射出成型直後にアルミラミジップ(アルミをPETでラミネートした袋)にノルボルネン系樹脂成型板を入れ、窒素パージし遮光して保存した。
・プライマー組成物の調製
1コート目のプライマー組成物は、上記プライマー組成物(硬化剤を除く)に、表1~3のそれぞれの硬化剤を混合し、希釈用シンナーにてイワタカップで測定される時間が10~60秒になるように粘度を調整した。
・上塗りの調製
2コート目の上塗りは、上記プライマー組成物(硬化剤を除く)に、表1~3に示されるイソシアネート系硬化剤を混合し、希釈用シンナーにてイワタカップで測定される時間が10~60秒になるように粘度を調整した。
上記作製したノルボルネン系樹脂成型板をアルミラミジップから取り出し、直ちにイソプロピルアルコールを用いて脱脂処理を行い、エアブローで乾燥後調製したプライマー組成物をスプレーガンで塗装した。
上記作製したノルボルネン系樹脂成型板をアルミラミジップから取り出し、塗装面を上にした状態で、屋外に3日間暴露した後、イソプロピルアルコールを用いて脱脂処理を行い、エアブローで乾燥後、調製したプライマー組成物をスプレーガンにて塗装した。
・1コート1ベークの場合
プライマー組成物を塗布後、室温で10~30分間セッティングし、次いで80℃×30分の強制乾燥を行い試験板とした。
・2コート2ベークの場合
プライマー組成物を塗布後、室温で10~30分間セッティングを行い、次いで80℃×30分の強制乾燥を行った。さらに、室温で60分間冷却後、上記上塗りを1コート1ベークと同様に塗装乾燥を行い試験板とした。
・2コート1ベークの場合
プライマー組成物を塗布後、室温で10~30分間セッティングし、上記上塗りを1コート1ベークと同様に塗装乾燥を行い試験板とした。
塗装完了後に試験板を常温で1週間放置し、その後、以下の評価を行った。結果を表4~6に示す。
それぞれの試験板を常温で1週間放置した後、JIS K5600-5.6クロスカット法に準じて2mm×2mmの升目を100個作成し、碁盤目剥離試験を実施し、以下の評価基準に従って評価した。
(評価基準)
◎:100~95個が剥離せずに残った。
○:94~80個が剥離せずに残った。
△:79~70個が剥離せずに残った。
×:剥離せずに残った数が69個以下であった。
それぞれの試験板を40℃の温水中に96時間浸漬し、その後、JIS K5600-5.6クロスカット法に準じて2mm×2mmの升目を100個作成し、碁盤目剥離試験を実施した。評価基準は、一次付着試験と同じ基準を採用した。
それぞれの試験板に対し、JIS K5600-7-2 耐湿性の条件にしたがって240時間試験を行った。その後、JIS K5600-5.6クロスカット法に準じて2mm×2mmの升目を100個作成し、碁盤目剥離試験を実施した。評価基準は、一次付着試験と同じ基準を採用した。
それぞれのプライマー組成物(硬化剤を除く)を、23℃で1週間放置した後、塗料の状態を目視で観察し、以下の評価基準に従って評価した。
(評価基準)
○:異常がなかった。
×:著しい沈殿が見られた。
Claims (9)
- エポキシ樹脂と、アミン系硬化剤とを含有し、
ノルボルネン系樹脂成型品の塗装に使用される、プライマー組成物。 - 特定顔料がさらに含有され、
前記エポキシ樹脂のエポキシ樹脂当量は、100~2500g/当量であり、
前記アミン系硬化剤の活性水素当量は、50~700g/当量であり、
前記エポキシ樹脂に含まれるエポキシ基1当量に対する前記アミン系硬化剤中の活性水素は、0.35~2.0当量であり、
前記プライマー組成物を前記ノルボルネン系樹脂成型品に塗装して得られる乾燥塗膜中における前記特定顔料の含有量は、0を超え、50重量%以下である、請求項1記載のプライマー組成物。 - 前記エポキシ樹脂のエポキシ樹脂当量は、100~2500g/当量であり、
前記アミン系硬化剤の活性水素当量は、50~700g/当量であり、
前記エポキシ樹脂に含まれるエポキシ基1当量に対する前記アミン系硬化剤中の活性水素は、0.35~2.0当量である、請求項1記載のプライマー組成物。 - 前記エポキシ樹脂は、ビスフェノールA型エポキシ樹脂およびビスフェノールF型エポキシ樹脂のうち、少なくともいずれか1つである、請求項1~3のいずれか1項に記載のプライマー組成物。
- 前記特定顔料は、タルク、クレーおよびマイカからなる群から選択される少なくともいずれか1つである、請求項2記載のプライマー組成物。
- 前記ノルボルネン系樹脂成型品は、湾曲した部分を有する樹脂成型品である、請求項1~5のいずれか1項に記載のプライマー組成物。
- エポキシ樹脂とアミン系硬化剤とを含有するプライマー組成物を、ノルボルネン系樹脂成型品に対して塗装する塗装工程を含む、塗装品の製造方法。
- 前記塗装工程は、前記ノルボルネン系樹脂成型品の表面を研磨することなく、前記プライマー組成物を塗装する工程である、請求項7記載の塗装品の製造方法。
- 前記塗装工程は、成型後に3日間以上屋外にて太陽光に曝露された前記ノルボルネン系樹脂成型品に対して行われる、請求項7または8記載の塗装品の製造方法。
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