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WO2017081963A1 - Kit de traitement de surface et article moulé composite et procédé pour les produire - Google Patents

Kit de traitement de surface et article moulé composite et procédé pour les produire Download PDF

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Publication number
WO2017081963A1
WO2017081963A1 PCT/JP2016/079741 JP2016079741W WO2017081963A1 WO 2017081963 A1 WO2017081963 A1 WO 2017081963A1 JP 2016079741 W JP2016079741 W JP 2016079741W WO 2017081963 A1 WO2017081963 A1 WO 2017081963A1
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WO
WIPO (PCT)
Prior art keywords
group
layer
molded body
liquid composition
groups
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Application number
PCT/JP2016/079741
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English (en)
Japanese (ja)
Inventor
豊 磯部
清治 水元
Original Assignee
株式会社ダイセル
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Priority to JP2017550028A priority Critical patent/JPWO2017081963A1/ja
Publication of WO2017081963A1 publication Critical patent/WO2017081963A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/47—Levelling agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/24—Di-epoxy compounds carbocyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • 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
    • 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
    • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
    • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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

Definitions

  • the present invention relates to a surface treatment kit for treating the surface of a molded body required to have slidability, heat resistance, etc., a composite molded body, and a method for producing the same.
  • An epoxy resin excellent in adhesiveness is used as a coating agent for treating the surface of various molded products.
  • Patent Document 1 after forming a wear-resistant first coating layer containing polyamideimide or polyimide and a solid lubricant, a first coating is formed on the first coating layer.
  • An internal combustion engine piston having a second coating layer formed of an epoxy resin having a lower hardness than the layer is disclosed.
  • the first coating layer is formed of polyamideimide or polyimide in order to improve wear resistance, compared to a conventional epoxy resin-based single layer coating containing fluororesin, which has excellent initial conformability. Yes.
  • Patent Document 2 discloses a photo-curing property that can be suitably used for automotive clear paints, plastic film top coat agents, plastic component protection coat agents, color filter protective film formation coat agents, and the like.
  • the resin composition an alicyclic diepoxy compound containing a 3,4,3′4′-diepoxybicyclohexyl compound, an epoxy compound other than the alicyclic diepoxy compound, an oxetane compound, a vinyl ether compound, an acrylic polymer, and A combination with at least one compound selected from the group consisting of bi- to hexa-functional polyol compounds is disclosed.
  • Patent Document 3 discloses that 3,4,3′4′-diepoxybicyclohexyl, a hydroxyl group-containing silicone compound and / or a silica filler are formed on at least one surface of a plastic substrate.
  • a hard coat film in which a hard coat layer formed of a curable composition containing an acid generator is laminated is disclosed.
  • this hard coat layer is formed on the surface of a plastic substrate, and this document does not intend to improve heat resistance.
  • alicyclic epoxy compounds are generally excellent in slidability and rigidity, but have low adhesion and adhesion. It has characteristics. Furthermore, slidability and adhesion are contradictory properties, and it has been difficult to achieve both properties.
  • JP-A-7-189804 (Claim 1, paragraphs [0002] [0003], Table 1)
  • JP 2008-189853 A (claim 1, paragraph [0014], example)
  • JP 2014-191173 A (Claim 1)
  • the object of the present invention was obtained by treating with a surface treatment kit capable of imparting slidability and heat resistance to the surface of the molded body, a laminate or a curable composition formed with this kit, and the kit. It is providing the composite molded object and its manufacturing method.
  • Another object of the present invention is to provide a surface treatment kit capable of forming a highly rigid film with high adhesion on the surface of a molded body by coating, a laminate or a curable composition formed with this kit, and treatment with the kit.
  • Another object of the present invention is to provide a composite molded body and a method for producing the same.
  • the present inventors combined the curable liquid composition containing a specific alicyclic epoxy compound and the liquid composition containing a polyamideimide resin to form a surface of the molded product.
  • the present inventors By processing, it discovered that slidability and heat resistance could be provided to the surface of a molded object, and completed this invention.
  • the surface treatment kit of the present invention is a surface treatment kit for treating the surface of a molded body formed of metal, and is represented by the formula (1)
  • R 1 to R 18 are the same or different and each represents a hydrogen atom, a halogen atom, an oxo group, a hydroxy group, a hydroperoxy group, an amino group, a sulfo group or an organic group, and X is a direct bond or Indicates a linking group
  • the curable liquid composition (A) containing the alicyclic epoxy compound represented by these, and the liquid composition (B) containing a polyamideimide resin are included.
  • the curable liquid composition (A) may further contain a curing agent and / or a leveling agent.
  • the liquid composition (B) may further contain at least one solid lubricant selected from the group consisting of fluorine compounds, metal sulfides, and carbon materials.
  • at least one of R 1 to R 18 may be a hydrogen atom, and X may be a direct bond.
  • the present invention also includes a laminate having a first layer containing a polyamideimide resin and a second layer containing a cured product of the curable liquid composition (A).
  • the indentation hardness by the microhardness meter of the second layer may be 300 N / mm 2 or more.
  • the arithmetic average roughness Ra of the surface of the second layer is about 1 to 100 nm.
  • the average thickness of the second layer may be about 2 to 100 times the average thickness of the first layer.
  • the present invention includes a composite including a molded body formed of metal and the laminated body laminated on the molded body, and the first layer of the laminated body is bonded or bonded to the molded body. A molded body is also included.
  • the metal may be an aluminum simple substance or an alloy containing aluminum.
  • This composite molded body may be a sliding member.
  • the composite molded body includes a first layer forming step of coating and solidifying the liquid composition (B) on the surface of a molded body formed of metal, and the curable liquid on the surface of the obtained first layer. It may be manufactured by a manufacturing method including a second layer forming step of coating and curing the composition (A).
  • the surface of the molded body is treated with a combination of a curable liquid composition containing a specific alicyclic epoxy compound and a liquid composition containing a polyamideimide resin, the surface of the molded body is slidable. And heat resistance. Furthermore, in spite of using an alicyclic epoxy compound with low adhesion, a combination with a polyamide-imide resin can form a highly rigid film on the surface of the molded body with high adhesion by coating.
  • the surface treatment kit of the present invention is a surface treatment kit for treating the surface of a molded body formed of metal, and includes a curable liquid composition (A) containing an alicyclic epoxy compound.
  • the alicyclic epoxy compound is represented by the formula (1).
  • examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. It is done.
  • the organic group is not particularly limited as long as it contains a carbon atom, for example, a hydrocarbon group, an alkoxy group, an alkenyloxy group, an aryloxy group, an aralkyloxy group, an acyl group, an acyloxy group, an alkylthio group, an alkenylthio group, Arylthio group, aralkylthio group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, aralkyloxycarbonyl group, epoxy group, epoxy-containing group, oxetanyl group, oxetanyl-containing group, cyano group, isocyanate group, carbamoyl group, isothiocyanate Examples thereof include a narate group and a substituted amino group.
  • hydrocarbon group examples include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group.
  • Examples of the aliphatic hydrocarbon group include an alkyl group, an alkenyl group, and an alkynyl group.
  • Examples of the alkyl group include C 1-20 alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, hexyl group, octyl group, isooctyl group, decyl group, and dodecyl group (preferably C 1-1 10 alkyl group, more preferably C 1-4 alkyl group).
  • alkenyl group examples include C 2-20 alkenyl groups such as vinyl group, allyl group, methallyl group, 1-propenyl group, isopropenyl group, butenyl group, pentenyl group, hexenyl group (preferably C 2-10 alkenyl group). And more preferably a C 2-4 alkenyl group).
  • alkynyl group examples include C 2-20 alkynyl groups such as ethynyl group and propynyl group (preferably C 2-10 alkynyl group, more preferably C 2-4 alkynyl group).
  • Examples of the alicyclic hydrocarbon group include a C 3-12 cycloalkyl group (particularly a C 5-8 cycloalkyl group) such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclododecyl group; a cyclohexenyl group And C 3-12 cycloalkenyl groups such as C 4-15 bridged cyclic hydrocarbon groups such as bicycloheptanyl group and bicycloheptenyl group.
  • a C 3-12 cycloalkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclododecyl group
  • C 3-12 cycloalkenyl groups such as C 4-15 bridged cyclic hydrocarbon groups such as bicycloh
  • aromatic hydrocarbon group examples include C 6-14 aryl groups (particularly C 6-10 aryl groups) such as a phenyl group and a naphthyl group.
  • alkoxy group examples include C 1-10 alkoxy groups such as methoxy group, ethoxy group, propoxy group, isopropyloxy group, butoxy group, isobutyloxy group (preferably C 1-6 alkoxy group, more preferably C 1-4 alkoxy group).
  • alkenyloxy group examples include a C 2-10 alkenyloxy group such as an allyloxy group (preferably a C 2-6 alkenyloxy group, more preferably a C 2-4 alkenyloxy group).
  • aryloxy group examples include a C 6-20 aryloxy group (particularly a C 6-14 aryloxy group) such as a phenoxy group, a tolyloxy group, and a naphthyloxy group.
  • aralkyloxy group examples include a C 7-20 aralkyloxy group (particularly a C 7-18 aralkyloxy group) such as a benzyloxy group and a phenethyloxy group.
  • acyl group examples include C 1-20 acyl groups such as acetyl group, propionyl group, (meth) acryloyl group, and benzoyl group (particularly, C 1-12 acyl group).
  • acyloxy group examples include C 1-20 acyloxy groups such as acetyloxy group, propionyloxy group, (meth) acryloyloxy group, and benzoyloxy group (particularly, C 1-12 acyloxy group).
  • alkylthio group examples include a C 1-6 alkylthio group such as a methylthio group and an ethylthio group (particularly a C 1-4 alkylthio group).
  • alkenylthio group examples include a C 2-6 alkenylthio group such as an allylthio group (particularly a C 2-4 alkenylthio group).
  • arylthio group examples include 6-20 arylthio groups (particularly C 6-14 arylthio groups) such as a phenylthio group, a tolylthio group, and a naphthylthio group.
  • aralkylthio group examples include a C 6-20 aralkylthio group (particularly a C 7-18 aralkylthio group) such as a benzylthio group and a phenethylthio group.
  • alkoxycarbonyl group examples include a C 1-10 alkoxy-carbonyl group such as a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, and a butoxycarbonyl group (particularly a C 1-6 alkoxy-carbonyl group).
  • aryloxycarbonyl group examples include a C 6-20 aryloxy-carbonyl group such as a phenoxycarbonyl group, a tolyloxycarbonyl group, and a naphthyloxycarbonyl group (particularly a C 6-14 aryloxy-carbonyl group).
  • aralkyloxycarbonyl group examples include a C 7-20 aralkyloxy-carbonyl group such as a benzyloxycarbonyl group (particularly a C 7-18 aralkyloxy-carbonyl group).
  • Examples of the epoxy-containing group include a glycidyl group and a glycidyloxy group.
  • Examples of the oxetanyl-containing group include a C 1-10 alkyl oxetanyloxy group such as an ethyl oxetanyloxy group.
  • substituted amino group examples include mono- or dialkylamino groups (particularly mono- or di-C 1-6 alkylamino groups) such as methylamino group, ethylamino group, dimethylamino group, and diethylamino group, acetylamino group, and propionylamino.
  • acylamino groups such as benzoylamino group (particularly C 1-11 acylamino group).
  • organic groups may be groups in which two or more organic groups are combined (bonded).
  • combinations of two or more organic groups include a combination of an aliphatic hydrocarbon group and an alicyclic hydrocarbon group (such as a cyclohexylmethyl group or a methylcyclohexyl group), an aliphatic hydrocarbon group, and an aromatic hydrocarbon.
  • a combination with a group [a C 7-18 aralkyl group such as a benzyl group or a phenethyl group (particularly a C 7-10 aralkyl group), a C 6-10 aryl-C 2-6 alkenyl group such as a cinnamyl group, a tolyl group, etc.
  • a combination with a group such as a methylphenoxy group
  • the organic group may further have a substituent.
  • substituents include a halogen atom, an oxo group, a hydroxy group, a hydroperoxy group, an amino group, and a sulfo group.
  • R 1 to R 18 a hydrogen atom, a linear or branched C 1-6 alkyl group (particularly, a linear C 1-3 alkyl group such as a methyl group), etc. are widely used and rigid
  • at least one of R 1 to R 18 is preferably a hydrogen atom, and all of them are particularly preferably hydrogen atoms.
  • examples of the linking group include a divalent hydrocarbon group, a carbonyl group, an ether bond, an ester bond, a carbonate bond, an amide bond, a urethane bond, and a group in which a plurality of these linking groups are connected.
  • the divalent hydrocarbon group includes a divalent aliphatic hydrocarbon group, a divalent alicyclic hydrocarbon group, and a divalent aromatic hydrocarbon group.
  • divalent aliphatic hydrocarbon group examples include an alkylene group, an alkenylene group, and an alkynylene group.
  • alkylene group examples include C 1 such as methylene group, ethylene group, propylene group, trimethylene group, butylene group, tetramethylene group, hexamethylene group, isohexylene group, octamethylene group, isooctylene group, decamethylene group, and dodecamethylene group. And a -20 alkylene group.
  • alkenylene group examples include C such as vinylene group, arylene group, metalrylene group, 1-propenylene group, isopropenylene group, 1-butenylene group, 2-butenylene group, butadienylene group, pentenylene group, hexenylene group, octenylene group, and the like. And a 2-20 alkenylene group.
  • the alkenylene group may be an alkenylene group in which part or all of the carbon-carbon double bond is epoxidized.
  • alkynylene group examples include C 2-20 alkynylene groups such as ethynylene group and propynylene group.
  • divalent alicyclic hydrocarbon group examples include a cyclopropylene group, a cyclobutylene group, a 1,2-cyclopentylene group, a 1,3-cyclopentylene group, a cyclopentylidene group, and a 1,3-cyclohexene group.
  • cyclohexylene 1,4-cyclohexylene group, cyclohexylidene group, cyclododecane - C 3-12 cycloalkylene groups (especially C 5-8 cycloalkylene group), such diyl group; C, such as cyclohexylene group 3 12 cycloalkenylene group; C 4-15 bridged cyclic hydrocarbon linking group such as bicycloheptanylene group and bicycloheptenylene group.
  • the divalent alicyclic hydrocarbon group may have an epoxy group, and may be, for example, an epoxy C 5-12 cycloalkylene group such as an epoxycyclohexylene group.
  • divalent aromatic hydrocarbon group examples include a C 6-14 arylene group such as a phenylene group and a naphthylene group.
  • These divalent hydrocarbon groups may have a substituent.
  • substituents include C 1-4 alkyl groups such as a methyl group and an ethyl group, C groups such as a methoxy group and an ethoxy group, in addition to the substituents exemplified as the substituents of the organic group in R 1 to R 18.
  • substituents include 1-4 alkoxy groups and carbonyl groups.
  • linking groups may be groups in which two or more linking groups are combined (bonded or connected).
  • a combination of two or more kinds of linking groups for example, a combination of a divalent aliphatic hydrocarbon group and a divalent alicyclic hydrocarbon group (for example, cyclohexylene methylene group, methylene cyclohexylene group, dicyclohexyl methane).
  • a combination of a divalent aliphatic hydrocarbon group and a divalent aromatic hydrocarbon group eg, a tolylene group, a xylylene group) , Diphenylmethane-4,4′-diyl group, diphenylpropane-4,4′-diyl group, etc.
  • a combination of an ester bond and a divalent hydrocarbon group for example, carbonyloxymethylene group, carbonyloxyhydrogenated xylylene Oxycarbonyl group
  • a combination of a carbonate bond and a divalent hydrocarbon group for example, methyleneoxycarboni) Oxymethylene group, methyleneoxycarbonyloxy hydrogenated xylyleneoxycarbonyloxymethylene group, etc.
  • a combination of a plurality of ester bonds for example, a polyester bond such as polycaprolact
  • X a direct bond, an alkylene group (C 1-4 alkylene group which may have a C 1-4 alkyl group such as a methylene group, a methylmethylene group, a dimethylmethylene group, an ethylene group, etc.)
  • An ether bond-containing group for example, C 1-4 alkyleneoxy C 1-4 alkylene group such as methyleneoxymethylene group
  • a combination of an ester bond and an alkylene group for example, carbonyloxy C 1 such as carbonyloxymethylene group
  • alkylene group a combination of a carbonate bond and an alkylene group (e.g., a C 1-4 alkylene oxy carbonyloxy C 1-4 alkylene group such as methylene oxycarbonyl oxymethylene group) are preferred, such as sliding property ( Direct bonding is particularly preferred because of its excellent surface smoothness and rigidity. Yes.
  • the alicyclic epoxy compound represented by the formula (1) may be only the same alicyclic epoxy compound, and a plurality of types of fats having different types of substituents R 1 to R 18 and / or group X It may be a combination of cyclic epoxy compounds.
  • Preferred alicyclic epoxy compounds include, for example, methyl groups such as 3,4,3 ′, 4′-diepoxybicyclohexyl and (3,4,3 ′, 4′-diepoxy-6-methyl) bicyclohexyl.
  • Diepoxybi C 5-8 cycloalkyl optionally having a C 1-4 alkyl group; 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexyl
  • Examples include alkane carboxylates. These alicyclic epoxy compounds can be used alone or in combination of two or more.
  • the curable liquid composition (A) preferably further contains a curing agent.
  • Curing agents include cationic polymerization initiators (acid generators) and conventional curing agents [for example, acid and acid anhydride curing agents, amine curing agents, polyaminoamide curing agents, imidazole curing agents, organic acid hydrazides. -Based curing agents, latent curing agents (such as dicyandiamides), polymercaptan-based curing agents, phenol-based curing agents, etc.].
  • cationic polymerization initiators (acid generators) and amine curing agents are widely used.
  • the cationic polymerization initiator includes a photoacid generator and a thermal acid generator depending on the type of polymerization.
  • the photoacid generator examples include a sulfonium salt (a salt of a sulfonium ion and an anion), an iodonium salt (a salt of an iodonium ion and an anion), a selenium salt (a salt of a selenium ion and an anion), and an ammonium salt (ammonium ion). And a phosphonium salt (a salt of a phosphonium ion and an anion), a salt of a transition metal complex ion and an anion, and the like.
  • These photoacid generators can be used alone or in combination of two or more.
  • an acid generator having a high acidity for example, a sulfonium salt is preferable from the viewpoint that the reactivity can be improved and the hardness of the cured product can be improved.
  • sulfonium salt examples include triphenylsulfonium salt, tri-p-tolylsulfonium salt, tri-o-tolylsulfonium salt, tris (4-methoxyphenyl) sulfonium salt, 1-naphthyldiphenylsulfonium salt, and 2-naphthyldiphenylsulfonium salt.
  • Tris (4-fluorophenyl) sulfonium salt tri-1-naphthylsulfonium salt, tri-2-naphthylsulfonium salt, tris (4-hydroxyphenyl) sulfonium salt, diphenyl [4- (phenylthio) phenyl] sulfonium salt, [4- (4-biphenylthio) phenyl] -4-biphenylphenylsulfonium salts, triarylsulfonium salts such as 4- (p-tolylthio) phenyldi- (p-phenyl) sulfonium salts; Diarylsulfonium salts such as nium salt, diphenyl 4-nitrophenacylsulfonium salt, diphenylbenzylsulfonium salt, diphenylmethylsulfonium salt; phenylmethylbenzylsulfonium salt, 4-
  • anion (counter ion) for forming a salt with the cation examples include SbF 6 ⁇ , PF 6 ⁇ , BF 4 ⁇ , fluorinated alkyl fluorophosphate ion [(CF 3 CF 2 ) 3 PF 3 ⁇ , ( CF 3 CF 2 CF 2 ) 3 PF 3- etc.], (C 6 F 5 ) 4 B ⁇ , (C 6 F 5 ) 4 Ga ⁇ , sulfonate anion (trifluoromethanesulfonate anion, pentafluoroethanesulfonate anion Nonafluorobutanesulfonate anion, methanesulfonate anion, benzenesulfonate anion, p-toluenesulfonate anion, etc.), (CF 3 SO 2 ) 3 C ⁇ , (CF 3 SO 2 ) 2 N ⁇ , perhalogen acid Ion, halogenated sulf
  • a commercially available photoacid generator can be used as the photoacid generator.
  • Examples of commercially available photoacid generators include “CPI-101A”, “CPI-110A”, “CPI-100P”, “CPI-110P”, “CPI-210S”, “CPI-200K” manufactured by San Apro Co., Ltd. Can be used.
  • thermal acid generator examples include arylsulfonium salts, aryliodonium salts, allene-ion complexes, quaternary ammonium salts, aluminum chelates, and boron trifluoride amine complexes. These thermal acid generators can be used alone or in combination of two or more. Among these thermal acid generators, an acid generator having a high acidity, for example, an arylsulfonium salt is preferable from the viewpoint that reactivity can be improved and hardness of the cured product can be improved.
  • the anion include the same anions as those of the photoacid generator, and may be an antimony fluoride ion such as SbF 6- .
  • thermal acid generator can also be used as the thermal acid generator.
  • thermal acid generators include “Sun-Aid SI-60L”, “Sun-Aid SI-60S”, “Sun-Aid SI-80L”, “Sun-Aid SI-100L” manufactured by Sanshin Chemical Industry Co., Ltd. ) "SP-66", “SP-77” manufactured by ADEKA can be used.
  • amine curing agent examples include aliphatic polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenediamine, diethylaminopropylamine, hexamethylenediamine, and polypropylenetriamine; mensendiamine, isophoronediamine, bis (4-amino-3-methyldicyclohexyl) methane, diaminodicyclohexylmethane, bis (aminomethyl) cyclohexane, N-aminoethylpiperazine, 3,9-bis (3-aminopropyl) -3,4,8,10-tetra Cycloaliphatic polyamines such as oxaspiro [5.5] undecane; m-phenylenediamine, p-phenylenediamine, tolylene-2,4-diamine, tolylene-2,6-diamine, mesitylene 2,4-d
  • amine curing agents can be used alone or in combination of two or more.
  • aliphatic polyamines ethylenediamine, diethylenetriamine, triethylenediamine, tetraethylenepentamine, diethylaminopropylamine, hexamethylenediamine, etc.
  • alicyclic polyamines mensendiamine, isophoronediamine, etc.
  • aromatic polyamines xylenediamine
  • Metaphenylenediamine etc.
  • cationic polymerization initiators are preferred because they can promote polymerization and improve the hardness of the cured product.
  • the proportion of the curing agent can be selected from a range of about 0.01 to 200 parts by weight (for example, 0.1 to 150 parts by weight) with respect to 100 parts by weight of the alicyclic epoxy compound depending on the type of the curing agent.
  • the proportion of the cationic polymerization initiator can be selected from the range of about 0.01 to 10 parts by weight, for example 0.05 to 5 parts by weight, preferably 0.1 to 3 parts by weight, based on 100 parts by weight of the alicyclic epoxy compound. Part, more preferably about 0.3 to 2 parts by weight (particularly 0.5 to 1.5 parts by weight). If the proportion of the cationic polymerization initiator is too small, the progress of the curing reaction may be reduced and the hardness of the cured product may be lowered. If the proportion is too large, the storage stability of the composition may be reduced, or the cured product may be colored. There is a fear.
  • the proportion of a conventional curing agent such as an amine-based curing agent may be, for example, about 50 to 200 parts by weight, preferably about 80 to 150 parts by weight with respect to 100 parts by weight of the alicyclic epoxy compound.
  • Leveling agent As the leveling agent, any conventional leveling agent (such as an ethylene oxide adduct of acetylene glycol) may be used as long as it has the ability to lower the surface tension. From the viewpoint of excellent surface tension reducing ability, a silicone leveling agent, Fluorine leveling agents are preferred. In the present invention, surface smoothness can be improved and slidability can be improved by combining the alicyclic epoxy compound and the leveling agent. Furthermore, not only can the hardness be maintained by using a specific leveling agent, but also the hardness can be improved by controlling the blending ratio.
  • the silicone leveling agent may be a leveling agent having a polyorganosiloxane skeleton.
  • the polyorganosiloxane skeleton includes a monofunctional M unit (generally represented by R 3 SiO 1/2 ) and a bifunctional D unit (generally represented by R 2 SiO 2/2 ). Unit), trifunctional T unit (generally expressed as RSiO 3/2 ), tetrafunctional Q unit (generally expressed as SiO 4/2 ), polyorgano Siloxane may be used, but polyorganosiloxane formed with D units is usually used.
  • the organic group (R) of the polyorganosiloxane can be selected from the hydrocarbon groups exemplified as R 1 to R 18 in the formula (1) of the alicyclic epoxy compound, and is usually C 1-4 alkyl. Groups and aryl groups are used, and methyl groups and phenyl groups (particularly methyl groups) are widely used.
  • the number of repeating siloxane units (degree of polymerization) is, for example, about 2 to 3000, preferably about 3 to 2000, and more preferably about 5 to 1000.
  • the fluorine-based leveling agent may be any leveling agent having a fluoroaliphatic hydrocarbon skeleton.
  • the fluoroaliphatic hydrocarbon skeleton include fluoroC 1-10 alkanes such as fluoromethane, fluoroethane, fluoropropane, fluoroisopropane, fluorobutane, fluoroisobutane, fluoro t-butane, fluoropentane, and fluorohexane. Can be mentioned.
  • fluoroaliphatic hydrocarbon skeletons it is sufficient that at least some of the hydrogen atoms are substituted with fluorine atoms, but from the viewpoint of improving slidability and rigidity, all of the hydrogen atoms are substituted with fluorine atoms.
  • a perfluoroaliphatic hydrocarbon skeleton is preferred.
  • the fluoroaliphatic hydrocarbon skeleton may form a polyfluoroalkylene ether skeleton that is a repeating unit via an ether bond.
  • the fluoroaliphatic hydrocarbon group as the repeating unit is at least one selected from the group consisting of fluoro C 1-4 alkylene groups such as a fluoromethylene group, a fluoroethylene group, a fluoropropylene group, and a fluoroisopropylene group. Also good.
  • These fluoroaliphatic hydrocarbon groups may be the same or a combination of plural kinds.
  • the number of repeating fluoroalkylene ether units (degree of polymerization) may be, for example, about 10 to 3000, preferably 30 to 1000, and more preferably about 50 to 500.
  • the polyorganosiloxane skeleton is preferable because of its excellent affinity with the cationic curable silicone resin.
  • the leveling agent having such a skeleton has various functionalities such as a hydrolytic condensable group, a functional group such as a reactive group with respect to an epoxy group, a radical polymerizable group, a polyether group, a polyester group, It may have a polyurethane group or the like. Further, the silicone leveling agent may have a fluoroaliphatic hydrocarbon group, and the fluorine leveling agent may have a polyorganosiloxane group.
  • hydrolyzable groups include hydroxysilyl groups; trihalosilyl groups such as trichlorosilyl groups; dihaloC 1-4 alkylsilyl groups such as dichloromethylsilyl groups; dihaloarylsilyl groups such as dichlorophenylsilyl groups; Haroji C 1-4 alkylsilyl group such as group; trimethoxysilyl group, tri C 1-4 alkoxysilyl group such as triethoxysilyl group; dimethoxymethylsilyl group, di-C 1-4 alkoxy such as diethoxymethyl silyl group C 1-4 alkylsilyl group; diC 1-4 alkoxyarylsilyl group such as dimethoxyphenylsilyl group and diethoxyphenylsilyl group; C1-4 alkoxydiC 1 ⁇ such as methoxydimethylsilyl group and ethoxydimethylsilyl group 4 alkylsilyl group; Metokishijifu Nirushir
  • Examples of the reactive group for the epoxy group include a hydroxyl group, an amino group, a carboxyl group, an acid anhydride group (such as a maleic anhydride group), and an isocyanate group.
  • a hydroxyl group, an amino group, an acid anhydride group, an isocyanate group and the like are widely used from the viewpoint of reactivity and the like, and a hydroxyl group is preferable from the viewpoint of handleability and availability.
  • radical polymerizable group examples include a (meth) acryloyloxy group and a vinyl group. Of these, (meth) acryloyloxy groups are widely used.
  • polyether group examples include polyoxy C 2-4 alkylene groups such as a polyoxyethylene group, a polyoxypropylene group, a polyoxybutylene group, and a polyoxyethylene-polyoxypropylene group.
  • the number of repeating oxyalkylene groups is, for example, about 2 to 1000, preferably about 3 to 100, and more preferably about 5 to 50.
  • polyoxyC 2-3 alkylene groups such as polyoxyethylene groups and polyoxypropylene groups (particularly polyoxyethylene groups) are preferred.
  • polyester group examples include a polyester group formed by a reaction between a dicarboxylic acid (an aromatic carboxylic acid such as terephthalic acid or an aliphatic carboxylic acid such as adipic acid) and a diol (an aliphatic diol such as ethylene glycol).
  • polyester groups formed by ring-opening polymerization of cyclic esters for example, lactones such as caprolactone).
  • polyurethane group examples include a conventional polyester type polyurethane group and a polyether type polyurethane group.
  • These functional groups may be directly bonded to the polyorganosiloxane skeleton or fluoroaliphatic hydrocarbon skeleton, and may be a linking group (for example, an alkylene group, a cycloalkylene group, an ether bond, an ester bond, An amide bond, a urethane bond, a linking group combining these, or the like).
  • a linking group for example, an alkylene group, a cycloalkylene group, an ether bond, an ester bond, An amide bond, a urethane bond, a linking group combining these, or the like.
  • a hydrolytic condensable group and a reactive group with respect to the epoxy group are preferred from the viewpoint of reacting with the alicyclic epoxy compound to improve the hardness of the cured product, and a reactive group with respect to the epoxy group ( Particularly preferred is a hydroxyl group.
  • the hydroxyl group may be a terminal hydroxyl group of a (poly) oxyalkylene group [(poly) oxyethylene group or the like].
  • a leveling agent for example, a silicone leveling agent in which a (poly) oxy C 2-3 alkylene group such as a (poly) oxyethylene group is introduced into a side chain of a polyorganosiloxane skeleton such as polydimethylsiloxane ( Fluorine leveling agents in which a fluoroaliphatic hydrocarbon group is introduced into the side chain of a (poly) oxy C 2-3 alkylene skeleton such as (polydimethylsiloxane polyoxyethylene) and (poly) oxyethylene (fluoroalkyl polyoxyethylene) Etc.).
  • a commercially available silicone leveling agent can be used as the silicone leveling agent.
  • examples of commercially available silicone leveling agents include BYK series leveling agents (“BYK-300”, “BYK-301 / 302”, “BYK-306”, “BYK-307”, manufactured by BYK Japan KK), “BYK-310”, “BYK-315”, “BYK-313”, “BYK-320”, “BYK-322”, “BYK-323”, “BYK-325”, “BYK-330”, “BYK” -331 ",” BYK-333 “,” BYK-337 “,” BYK-341 ",” BYK-344 “,” BYK-345 / 346 ",” BYK-347 “,” BYK-348 “,” BYK -349 ",” BYK-370 “,” BYK-375 “,” BYK-377 “,” BYK-378 “,” BYK-UV3500 “,” BYK-UV3 " 10 ”,“ B
  • KP series leveling agents KP-323 “,” KP-326 “,” KP-341 “,” KP-104 “, “KP-110”, “KP-112”, etc.
  • Toray Da Leveling agents LP-7001”, “LP-7002”, “8032ADDITIVE”, “57ADDITIVE”, “L-7604”, “FZ-2110”, “FZ-2105”, “67ADDITIVE”, manufactured by Corning Corp., "8618ADDITIVE”, “3ADDITIVE”, “56ADDITIVE”, etc.).
  • a commercially available fluorine leveling agent can be used as the fluorine leveling agent.
  • commercially available fluorine-based leveling agents include leveling agents ("DSX” and “DAC-HP”) manufactured by Daikin Industries, Ltd., and Surflon series leveling agents (“DSX” and “DAC-HP") manufactured by AGC Seimi Chemical Co., Ltd. S-242 ",” S-243 “,” S-420 “,” S-611 “,” S-651 “,” S-386 “, etc.), BYK series leveling agents manufactured by Big Chemie Japan K.K.
  • PF series leveling agents (“ PF-136A “,” PF-156A “,” PF-151N ”,“ PF-636 ”,“ PF-6320 ”,“ PF-656 ”,“ PF-6520 ”,“ PF-651 ”,“ PF-652 ”,“ PF-3320 ”, etc.) Can be mentioned.
  • leveling agents can be used alone or in combination of two or more.
  • a plurality of types of silicone leveling agents and a plurality of types of fluorine leveling agents may be combined. Silicone leveling agents and fluorine leveling agents And may be used in combination.
  • a silicone-based leveling agent having a hydroxyl group is preferable because it has excellent affinity with an alicyclic epoxy compound, can react with an epoxy group, and can improve the hardness and appearance of a cured product.
  • silicone-based leveling agent having a hydroxyl group examples include a polyether-modified polyorganosiloxane having a polyether group introduced into the main chain or side chain of a polyorganosiloxane skeleton (such as polydimethylsiloxane) or the main chain of a polyorganosiloxane skeleton.
  • a polyether-modified polyorganosiloxane having a polyether group introduced into the main chain or side chain of a polyorganosiloxane skeleton such as polydimethylsiloxane
  • transduced the polyorganosiloxane to the (meth) acrylic resin, etc. are mentioned.
  • the hydroxyl group may have a polyorganosiloxane skeleton, or a polyether group, a polyester group, or a (meth) acryloyl group.
  • a leveling agent for example, “BYK-370”, “BYK-SILCLEAN3700”, “BYK-SILCLEAN3720” manufactured by Big Chemie Japan Co., Ltd. can be used.
  • the ratio of the leveling agent can be selected from the range of about 0.01 to 20 parts by weight with respect to 100 parts by weight of the alicyclic epoxy compound, for example, 0.05 to 15 parts by weight, preferably 0.1 to 10 parts by weight, More preferably, it is about 0.2 to 5 parts by weight. If the ratio of the leveling agent is too small, the slidability of the cured product may be reduced, and if too high, the hardness of the cured product may be reduced.
  • the ratio of the silicone leveling agent is, for example, 0.1 to 10 parts by weight, preferably 0.2 to 5 parts by weight, and more preferably 0.3 to 3 parts by weight with respect to 100 parts by weight of the alicyclic epoxy compound. Part (especially 0.5 to 2 parts by weight).
  • the ratio of the fluorine leveling agent is, for example, 0.05 to 5 parts by weight, preferably 0.1 to 3 parts by weight, more preferably 0.2 to 1 part by weight (100 parts by weight based on 100 parts by weight of the alicyclic epoxy compound. In particular, it may be about 0.3 to 0.8 part by weight).
  • the curable liquid composition (A) may contain another curable resin.
  • curable resins include other epoxy resins (epoxy resins other than alicyclic epoxy compounds), oxetane resins, vinyl ether resins, and the like. These curable resins can be used alone or in combination of two or more. Among these curable resins, other epoxy resins are preferable in terms of reactivity and miscibility. Examples of the other epoxy resins include glycidyl ether type epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, and long chain aliphatic epoxy resins.
  • the ratio of the other curable resin is about 100 parts by weight or less with respect to 100 parts by weight of the alicyclic epoxy compound, for example, 50 parts by weight or less (for example, 1 to 50 parts by weight), preferably 30 parts by weight or less. (For example, about 5 to 30 parts by weight).
  • the curable liquid composition (A) may contain a conventional additive as long as it does not impair slidability and rigidity.
  • conventional additives include curing accelerators (imidazoles, alkali metal or alkaline earth metal alkoxides, phosphines, amide compounds, Lewis acid complex compounds, sulfur compounds, boron compounds, condensable organometallic compounds, etc.) Fillers (inorganic fillers such as titanium oxide and alumina), stabilizers (antioxidants, UV absorbers, light stabilizers, heat stabilizers, etc.), plasticizers, lubricants, antifoaming agents, antistatic agents, It may contain a flame retardant. These additives can be used alone or in combination of two or more.
  • the total proportion of these additives is about 100 parts by weight or less with respect to 100 parts by weight of the alicyclic epoxy compound, for example, 30 parts by weight or less (eg, 0.01 to 30 parts by weight), preferably 10 parts by weight or less. (For example, 0.1 to 10 parts by weight).
  • the curable liquid composition (A) is an organic solvent such as ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), ethers (dioxane, tetrahydrofuran, etc.), aliphatic hydrocarbons (hexane, etc.).
  • ketones acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.
  • ethers dioxane, tetrahydrofuran, etc.
  • aliphatic hydrocarbons hexane, etc.
  • Alicyclic hydrocarbons (cyclohexane, etc.), aromatic hydrocarbons (benzene, toluene, etc.), halogenated carbons (dichloromethane, dichloroethane, etc.), esters (methyl acetate, ethyl acetate, etc.), water, alcohols (Ethanol, isopropanol, butanol, cyclohexanol, etc.), cellosolves (methyl cellosolve, ethyl cellosolve, etc.), cellosolve acetates, amides (dimethylformamide, dimethylacetamide, etc.) and the like may be contained. These solvents can be used alone or in combination of two or more.
  • the solid content weight of the curable liquid composition (A) can be arbitrarily selected according to the process of the molding process, and is not particularly limited, in order to adjust the viscosity of the liquid composition suitable for the process.
  • the liquid composition (B) contains a polyamideimide resin, and the polyamideimide resin can improve the heat resistance of the coating layer covering the molded body, and can also improve the adhesion to the metal molded body.
  • the polyamideimide resin is a polymer having an imide bond and an amide bond in the main chain, and a polyamideimide obtained by reacting a tricarboxylic acid anhydride (or a reactive derivative such as a halide or a lower alkyl ester thereof) with a polyvalent isocyanate, It may be a polyamideimide formed by reacting a tricarboxylic acid anhydride with a polyvalent amine to form an imide bond and then amidating with a polyisocyanate.
  • Polyamideimide resin is usually a resin obtained by using trimellitic anhydride as the tricarboxylic acid anhydride, for example, the formula (2)
  • Y represents a group containing a divalent hydrocarbon group
  • the resin which has a repeating unit represented by these may be sufficient.
  • examples of the divalent hydrocarbon group include the divalent hydrocarbon groups exemplified as X in the formula (1).
  • the divalent hydrocarbon group may be a C 1-10 alkylene group such as an ethylene group or a C 5-8 cycloalkylene group such as a cyclohexylene group, but from the viewpoint of heat resistance, a phenylene group or a naphthylene group.
  • a group containing a divalent aromatic hydrocarbon group is a direct bond; an alkylene group (for example, a C 1-4 alkylene group such as a methylene group, an ethylene group, a dimethylmethylene group (propane-2,2-diyl group), etc.)
  • a divalent aromatic hydrocarbon group and an alkylene group are substituted (for example, a C 1-4 alkyl group such as a methyl group or an ethyl group, a C 1-4 alkoxy group such as a methoxy group or an ethoxy group, A halogen atom such as a chlorine atom or a fluorine atom, or a hydroxyl group).
  • Examples of Y include a phenylene group (1,4-phenylene group, 1,3-phenylene group, etc.), a naphthylene group (1,5-naphthylene group, 2,6-naphthylene group, etc.), a biphenylene group (4,4 '-Biphenylene group, 3,3'-biphenylene group, etc.), bisphenol residue [diphenylmethane-4,4'-diyl group (bisphenol F residue), dimethyldiphenylmethane-4,4'-diyl group (bisphenol A residue) ), Diphenylcarbonyl-4,4′-diyl group, diphenylsulfonyl-4,4′-diyl group (bisphenol S residue), diphenylthio-4,4′-diyl group, diphenyloxy-4,4′-diyl Group, etc.], or these groups are further directly bonded or linking groups (carbonyl group,
  • phenylene groups, biphenylene groups, bisphenol residues, etc. are widely used, and substituents (halogen atoms such as fluorine atoms and chlorine atoms, C 1-3 alkyl groups such as methyl groups, C groups such as methoxy groups, etc.) are added to the benzene ring.
  • substituents halogen atoms such as fluorine atoms and chlorine atoms, C 1-3 alkyl groups such as methyl groups, C groups such as methoxy groups, etc.
  • a biphenylene group or a diphenylmethane-4,4′-diyl group (bisphenol F residue) which may have a 1-3 alkoxy group or the like is preferable.
  • the number average molecular weight of the polyamideimide resin is, for example, 1,000 or more in terms of polystyrene in gel permeation chromatography (GPC), for example, 3,000 to 500,000, preferably 5,000 to 300,000, Preferably, it is about 8,000 to 100,000 (particularly 10,000 to 50,000). If the molecular weight is too small, heat resistance and mechanical properties may be reduced.
  • GPC gel permeation chromatography
  • the glass transition temperature of the polyamide-imide resin may be 150 ° C. or higher, for example, 180 to 400 ° C., preferably 200 to 380 ° C., more preferably 250 to 350 ° C. (especially 280 to 330 ° C.). If the glass transition temperature is too low, the heat resistance may be reduced. In the present invention, the glass transition temperature of the polyamideimide resin can be measured using a differential scanning calorimeter (DSC).
  • DSC differential scanning calorimeter
  • the liquid composition (B) may contain a solid lubricant in addition to the polyamideimide resin.
  • the solid lubricant include conventional solid lubricants such as fluorine compounds (fluorine resins such as polytetrafluoroethylene, fluorinated graphite), boron compounds (such as boron nitride), and sulfides such as metal sulfides (such as molybdenum disulfide). Examples thereof include molybdenum, tungsten sulfide such as tungsten disulfide), carbon materials (such as graphite and carbon black), simple metals (such as silver, lead, and nickel), mica, organic molybdenum compounds, and melamine cyanurate.
  • fluorine compounds fluorine resins such as polytetrafluoroethylene, fluorinated graphite
  • boron compounds such as boron nitride
  • sulfides such as metal sulfides (such as molybdenum dis
  • solid lubricants can be used alone or in combination of two or more.
  • fluorine compounds particularly polytetrafluoroethylene
  • metal sulfides particularly molybdenum disulfide
  • carbon materials particularly graphite
  • the ratio of the solid lubricant is about 500 parts by weight or less (for example, 0.1 to 500 parts by weight, preferably 10 to 200 parts by weight) with respect to 100 parts by weight of the polyamideimide resin. If the ratio of the solid lubricant is too large, the mechanical properties of the solidified coating film may be deteriorated.
  • the liquid layer composition (B) may contain a solid lubricant at the above-mentioned ratio depending on the use, but it is preferable not to contain a solid lubricant from the viewpoint of adhesion to the substrate.
  • the liquid composition (B) may also contain other additives as long as the heat resistance and slidability are not impaired.
  • Conventional additives include curing agents (such as epoxy resins), fillers (such as inorganic fillers such as titanium oxide and alumina), stabilizers (antioxidants, UV absorbers, light stabilizers, heat stabilizers, etc.) ), Plasticizers, antifoaming agents, antistatic agents, flame retardants, and the like. These additives can be used alone or in combination of two or more.
  • the ratio of these additives is about 100 parts by weight or less with respect to 100 parts by weight of the polyamideimide resin, for example, 30 parts by weight or less (for example, 0.01 to 30 parts by weight), preferably 10 parts by weight or less (for example, 0.1 to 10 parts by weight).
  • the liquid composition (B) may be an organic solvent such as an amide (for example, N-mono or di C 1-4 alkylformamide such as N-methylformamide, N, N-dimethylformamide; N-methylacetamide, N-mono or di-C 1-4 alkylacetamide such as N, N-dimethylacetamide; N-methylpyrrolidone etc.), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone etc.), ethers (dioxane, tetrahydrofuran etc.) , Aliphatic hydrocarbons (such as hexane), alicyclic hydrocarbons (such as cyclohexane), aromatic hydrocarbons (such as benzene and toluene), halogenated carbons (such as dichloromethane and dichloroethane), esters (methyl acetate) , Ethyl acetate, etc.
  • the solid content weight of the liquid composition (B) can be arbitrarily selected according to the process of the molding step to adjust the viscosity of the liquid composition suitable for the step, and is not particularly limited. It can be selected from a range of about wt%.
  • the surface of the molded body may be treated using the surface treatment kit, and the curable liquid composition obtained by mixing the curable liquid composition (A) and the liquid composition (B) is coated.
  • a first layer a heat-resistant layer or a primer layer
  • a second product containing a cured product of the curable liquid composition (A). It is preferable to form a laminate having a layer (sliding layer or topcoat layer).
  • the manufacturing method of this laminated body is not particularly limited, and the second layer and the first layer, which are independently manufactured, may be integrated via an adhesive layer or the like, but the first layer adheres to the second layer. Since the property is excellent, the surface of the first layer obtained by coating and solidifying the liquid composition (B) is coated with the curable liquid composition (A) and cured to form the second layer.
  • the forming method is preferred.
  • the second layer has a high hardness and may have an indentation hardness of 300 N / mm 2 or more (for example, 300 to 1000 N / mm 2 ), preferably 450 N / mm 2 or more (for example, 450 to 800 N / mm). mm 2 ), more preferably 550 N / mm 2 or more (for example, about 550 to 700 N / mm 2 ). If the indentation hardness is too small, it may be difficult to maintain the wear resistance of the second layer for a long period of time. In addition, in this invention, indentation hardness can be measured by the method as described in the Example mentioned later.
  • the surface of the second layer is excellent in smoothness, and the arithmetic average roughness Ra based on JIS B0601 (2001) may be 100 nm or less (for example, 1 to 100 nm), for example, 2 to 50 nm, preferably 3 It is about 30 nm (for example, 4-20 nm), more preferably about 5-15 nm (especially 7-10 nm).
  • a combination of the polyamideimide resin contained in the first layer and the alicyclic epoxy compound represented by (1) contained in the second layer especially an alicyclic epoxy compound in which X is a direct bond).
  • the average thickness of the first layer may be, for example, 0.5 ⁇ m or more, for example, 0.5 to 30 ⁇ m, preferably 0.8 to 10 ⁇ m, and more preferably 1 to 5 ⁇ m (especially 1.5 to 3 ⁇ m). is there. If the first layer is too thin, heat resistance and adhesion to the metal molded body and the second layer may be reduced.
  • the average thickness of the second layer may be 1 ⁇ m or more, for example, 1 to 100 ⁇ m, preferably 5 to 80 ⁇ m, and more preferably about 10 to 50 ⁇ m. If the second layer is too thin, the slidability and rigidity may be reduced.
  • the average thickness of the first layer and the second layer can be measured as an average value at any 10 locations using, for example, an optical film thickness meter.
  • the composite molded body of the present invention includes a molded body formed of a metal and the laminated body laminated on the molded body, and the first layer of the laminated body is bonded or adhered to the molded body. .
  • the first layer of the laminate is excellent not only in adhesion to the second layer but also in adhesion to the molded body, and can be joined to the molded body without interposing an adhesive layer. Therefore, the composite molded body of the present invention is a first layer forming step of coating and solidifying the liquid composition (B) on the surface of the molded body formed of metal, on the surface of the obtained first layer, You may manufacture through the 2nd layer formation process which coats and hardens
  • the liquid composition (B) is coated by a conventional method such as roll coating, air knife coating, blade coating, rod coating, reverse coating, bar coating, comma coating, die coating, gravure.
  • a conventional method such as roll coating, air knife coating, blade coating, rod coating, reverse coating, bar coating, comma coating, die coating, gravure.
  • Examples include coating, screen coating method, spray method, spinner method and the like.
  • a blade coating method, a bar coating method, a gravure coating method and the like are widely used.
  • the method of solidifying the liquid composition (B) may be natural drying, but the method of heating and drying is preferred from the viewpoint of improving the strength of the first layer and the adhesion to the molded body.
  • the heating temperature for drying may be, for example, about 60 ° C. or higher (for example, 60 to 300 ° C.).
  • the solidification method of the liquid composition (B) is particularly preferably a method of further baking after heating and drying (preheating) from the viewpoint that the strength of the first layer and the adhesion to the molded body can be further improved. preferable.
  • the preheating temperature is, for example, about 40 to 150 ° C., preferably 50 to 120 ° C., more preferably about 60 to 100 ° C. (especially 70 to 90 ° C.).
  • the preheating time may be about 3 minutes or more (for example, 3 minutes to 2 hours), preferably 5 minutes or more (for example, 5 minutes to 1 hour), more preferably about 8 minutes or more (for example, 8 to 30 minutes). .
  • the calcination temperature may be 120 ° C. or higher, for example, 120 to 300 ° C., preferably 150 to 280 ° C., more preferably 160 to 250 ° C. (especially 180 to 230 ° C.). If the firing temperature is too low, the strength of the first layer and the adhesion to the molded body may be reduced.
  • the firing time is 1 minute or longer (for example, 1 minute to 3 hours), preferably 10 minutes or longer (for example, 10 minutes to 2 hours), and more preferably 30 minutes or longer (for example, 30 minutes to 1.5 hours).
  • the baking treatment for forming the first layer may be a heat treatment for forming the second layer in the second layer forming step (for example, an aging treatment in the second layer forming step described later), In that case, the aging treatment for forming the second layer also serves as the firing treatment for the first layer. From the viewpoint that the surface smoothness of the second layer can be improved, the firing treatment for forming the first layer is preferably performed in the first layer forming step, not in the second layer forming step.
  • the same coating method as in the first layer forming step can be used, and a blade coater method, a bar coater method, a gravure coater method, etc. are widely used. Is done.
  • the curable liquid composition (A) may be heated and dried (preliminary heating) before the curing treatment.
  • the preheating temperature is, for example, about 40 to 150 ° C., preferably 50 to 120 ° C., more preferably 60 to 100 ° C. (especially 70 to 90 ° C.).
  • the preheating time may be 10 seconds or longer (for example, 10 seconds to 10 minutes), preferably 20 seconds or longer (for example, 20 seconds to 5 minutes), and more preferably 30 seconds or longer (for example, 30 seconds to 2 minutes). Good.
  • the curable liquid composition (A) may be cured by irradiating an active energy ray depending on the kind of the curing agent, or may be cured by heating. Among these, it can be usually cured by irradiating with active energy rays.
  • Heat and / or light energy rays can be used as the active energy rays, and it is particularly useful to irradiate light using the light energy rays.
  • As light energy rays radiation (gamma rays, X-rays, etc.), ultraviolet rays, visible rays, electron beams (EB), etc. can be used, and usually ultraviolet rays and electron beams are often used.
  • irradiation with an electron beam may be performed.
  • a Deep UV lamp for example, in the case of ultraviolet rays, a Deep UV lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a halogen lamp, a laser light source (light source such as helium-cadmium laser or excimer laser), etc. may be used. it can.
  • Irradiation light amount varies depending on the thickness of the coating film, for example, 50 ⁇ 10000mJ / cm 2, preferably 70 ⁇ 5000mJ / cm 2, more preferably may be 100 ⁇ 1000mJ / cm 2 approximately.
  • the light amount and the irradiation time may be increased.
  • the irradiation light amount is, for example, 300 to 10,000 mJ / cm 2 (particularly 400 to 3000 mJ / cm 2 ). It may be a degree.
  • a method of irradiating an electron beam with an exposure source such as an electron beam irradiation apparatus can be used.
  • the irradiation amount (dose) varies depending on the thickness of the coating film, but is, for example, about 1 to 200 kGy (gray), preferably 5 to 150 kGy, more preferably 10 to 100 kGy (especially 20 to 80 kGy).
  • the acceleration voltage is, for example, about 10 to 1000 kV, preferably about 50 to 500 kV, and more preferably about 100 to 300 kV.
  • Irradiation with active energy rays may be performed in an inert gas (for example, nitrogen gas, argon gas, helium gas, etc.) atmosphere if necessary.
  • an inert gas for example, nitrogen gas, argon gas, helium gas, etc.
  • the heating temperature is, for example, about 30 to 250 ° C., preferably 50 to 220 ° C., more preferably 60 to 200 ° C. (particularly 120 to 160 ° C.).
  • the heating time is, for example, about 10 minutes to 10 hours, preferably about 30 minutes to 5 hours, and more preferably about 45 minutes to 3 hours.
  • the heating temperature is, for example, about 30 to 200 ° C, preferably about 50 to 190 ° C, and more preferably about 60 to 180 ° C.
  • a curing treatment using active energy rays such as ultraviolet rays is preferable because it can be used for a wide range of supports.
  • the metal forming the molded body to be processed by the surface treatment kit is not particularly limited, and examples thereof include aluminum, iron, nickel, copper, and chromium.
  • the metal may be the single metal or an alloy of the metal (for example, stainless steel or steel).
  • the metal surface may be subjected to plating treatment such as galvanization for rust prevention treatment.
  • metals containing aluminum and iron are widely used, and metals containing aluminum (such as aluminum alone or aluminum alloys) are preferable.
  • Alicyclic epoxy compound A 3,4,3 ′, 4′-diepoxybicyclohexyl
  • Alicyclic epoxy compound B 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate, Daicel Corporation “Celoxide 2021P” Bisphenol A type epoxy resin: “jER828” manufactured by Mitsubishi Chemical Corporation (Resin for primer layer)
  • Polyamideimide A “Viromax HR-11NN” manufactured by Toyobo Co., Ltd.
  • Polyamideimide B “Dry coat 3500” manufactured by Sumiko Lubricant Co., Ltd.
  • Acrylic oligomer “Ray Magic” manufactured by Kana Sakai Paint Co., Ltd.
  • Curing agent [4- (4-biphenylthio) phenyl] -4-biphenylphenylsulfonium tris (pentafluoroethyl) trifluorophosphate
  • Leveling agent Polyether-modified polydimethylsiloxane solution having a hydroxyl group, manufactured by BYK Japan Co., Ltd. “BYK-SILCLEAN3720”.
  • Adhesion (cross-cut method)
  • the adhesion of the coating film that has been coated and hardened on the aluminum plate is made by making 25 squares of 2 mm x 2 mm on the painted surface, 5 squares x 5 squares, and sticking an adhesive cellophane tape on the surface. After peeling, the adhesiveness was simply evaluated by counting the number of squares in which 80% or more of the total area remained out of 25 squares.
  • Measurement mode Load-unload mode
  • Example 1 Polyamideimide A was applied as a primer layer (first layer) on an aluminum plate degreased with acetone using wire bar # 3, preheated (prebaked) at 80 ° C. for 15 minutes, and then 200 ° C. Baked for 60 minutes.
  • top coat layer 100 parts by weight of alicyclic epoxy compound A, 0.25 parts by weight of curing agent and 1 part by weight of leveling agent were applied using wire bar # 20.
  • pre-baking was performed at 80 ° C. for 1 minute, and then using a belt conveyor type high-pressure mercury lamp (“UVC-02516S1” manufactured by USHIO INC.), A 120 W lamp output and a conveyor speed of 5.5 m / min. And processed with ultraviolet rays having an integrated light quantity of 400 mJ / cm 2 .
  • the coating film of the topcoat layer was cured by heat treatment (aging treatment) at 150 ° C. for 1 hour, and a composite molded body (painted aluminum plate) having a primer layer and a topcoat layer was produced.
  • the average thickness of the coating film was 37 ⁇ m.
  • Example 2 A composite molded body was produced in the same manner as in Example 1 except that the treatment temperature of the aging treatment of the topcoat layer was changed to 200 ° C. The average thickness of the coating film was 36 ⁇ m.
  • Example 3 Polyamideimide A was applied as a primer layer (first layer) on an aluminum plate degreased with acetone using wire bar # 3, and then heated at 80 ° C. for 60 minutes.
  • top coat layer 100 parts by weight of alicyclic epoxy compound A, 0.25 parts by weight of curing agent and 1 part by weight of leveling agent were applied using wire bar # 20.
  • pre-baking was performed at 80 ° C. for 1 minute, and then using a belt conveyor type high-pressure mercury lamp (“UVC-02516S1” manufactured by USHIO INC.), A 120 W lamp output and a conveyor speed of 5.5 m / min. And processed with ultraviolet rays having an integrated light quantity of 400 mJ / cm 2 .
  • the coating film of the topcoat layer is cured by further heat treatment at 200 ° C. for 1 hour, and a composite molded body having a primer layer and a topcoat layer ( A painted aluminum plate) was prepared.
  • the average thickness of the coating film was 31 ⁇ m.
  • Example 4 A composite molded body was produced in the same manner as in Example 3 except that the aging treatment of the topcoat layer was changed to 200 ° C. for 1 hour. The average thickness of the coating film was 36 ⁇ m.
  • Example 5 A composite molded body was produced in the same manner as in Example 1 except that polyamideimide B was used instead of polyamideimide A.
  • the average thickness of the coating film was 29 ⁇ m.
  • Example 6 A composite molded body was produced in the same manner as in Example 1 except that the alicyclic epoxy compound B was used instead of the alicyclic epoxy compound A.
  • the average thickness of the coating film was 31 ⁇ m.
  • Comparative Example 2 A composite molded body was produced in the same manner as in Comparative Example 1 except that the alicyclic epoxy compound B was used instead of the alicyclic epoxy compound A.
  • the average thickness of the coating film was 26 ⁇ m.
  • Comparative Example 3 A composite molded body was produced in the same manner as in Comparative Example 1 except that a bisphenol A type epoxy resin was used in place of the alicyclic epoxy compound A. The average thickness of the coating film was 32 ⁇ m.
  • Comparative Example 4 After applying 100 parts by weight of an alicyclic epoxy compound A, 0.25 parts by weight of a curing agent and 1 part by weight of a leveling agent as a top coat layer on an aluminum plate degreased with acetone using a wire bar # 20, Pre-baked at 1 ° C. for 1 minute, and then irradiated with ultraviolet rays at a conveyor speed of 5.5 m / min with a 120 W lamp output using a belt conveyor type high-pressure mercury lamp (“UVC-02516S1” manufactured by USHIO INC.) It processed with the ultraviolet-ray of integrated light quantity 400mJ / cm ⁇ 2 >. Finally, the coating film of the topcoat layer was cured by heat treatment (aging treatment) at 150 ° C. for 1 hour, and a composite molded body (painted aluminum plate) having only the topcoat layer was produced. The average thickness of the coating film (thickness only of the topcoat layer) was 37 ⁇ m.
  • Comparative Example 5 A composite molded body was produced in the same manner as in Example 1 except that a bisphenol A type epoxy resin was used instead of the alicyclic epoxy compound A. The average thickness of the coating film was 38 ⁇ m.
  • a topcoat layer was formed on the obtained primer layer in the same manner as in Example 1 to produce a composite molded body.
  • the average thickness of the coating film was 38 ⁇ m.
  • Table 1 shows the results of evaluating the composite molded bodies obtained in Examples and Comparative Examples.
  • the composite molded bodies of the examples had high adhesion and heat resistance, and had excellent surface smoothness.
  • the composite molded bodies of Comparative Examples 1 to 4 had low adhesion
  • the composite molded body of Comparative Example 5 had low indentation hardness
  • the composite molded body of Comparative Example 6 had low heat resistance.
  • the surface treatment kit of the present invention can be used as a surface treatment agent for coating various molded products (two-dimensional or three-dimensional molded products) formed of a metal that is required to have slidability and heat resistance. It can be effectively used as a surface treatment agent for various industrial equipment, transportation equipment such as automobiles and airplanes, electronic and electrical equipment members (for example, sliding members such as cylinders, pistons, and bearings).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Laminated Bodies (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Paints Or Removers (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

Abstract

L'invention concerne le traitement de la surface d'un article métallique moulé à l'aide d'un kit de traitement de surface qui comprend une composition liquide durcissable (A) contenant un composé époxy alicyclique représenté par la formule (1) et une composition liquide (B) contenant une résine polyamide-imide permettant de conférer une capacité de glissement et une résistance à la chaleur à la surface de l'article moulé. (Dans la formule, R1-R18 sont identiques ou différents et représentent un atome d'hydrogène, un atome d'halogène, un groupe oxo, un groupe hydroxy, groupe hydroperoxy, un groupe amino, un groupe sulfo ou un groupe organique ; et X représente une liaison directe ou un groupe de liaison)
PCT/JP2016/079741 2015-11-10 2016-10-06 Kit de traitement de surface et article moulé composite et procédé pour les produire WO2017081963A1 (fr)

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Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6067531A (ja) * 1983-09-22 1985-04-17 Toshiba Corp 樹脂組成物
JPS6071631A (ja) * 1983-09-29 1985-04-23 Toshiba Corp 光硬化性組成物
JPH07189804A (ja) * 1993-12-27 1995-07-28 Toyota Motor Corp 内燃機関のピストンおよびその製造方法
JPH08217813A (ja) * 1995-02-17 1996-08-27 Toyo Ink Mfg Co Ltd 光開始剤組成物、光重合性組成物および光重合方法
JPH09143248A (ja) * 1995-11-20 1997-06-03 Toyo Ink Mfg Co Ltd 紫外線硬化型樹脂組成物およびこれを含む被覆剤
JPH11349895A (ja) * 1998-06-08 1999-12-21 Kansai Paint Co Ltd カチオン重合性塗料組成物
JP2008189853A (ja) * 2007-02-06 2008-08-21 Daicel Chem Ind Ltd 光硬化性樹脂組成物及び塗装物
JP2015185504A (ja) * 2014-03-26 2015-10-22 日立金属株式会社 エナメル線の製造方法
JP2016120476A (ja) * 2014-12-25 2016-07-07 トヨタ自動車株式会社 摺動部材およびその製造方法
JP2016121314A (ja) * 2014-12-25 2016-07-07 株式会社ダイセル 耐摩耗剤

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6067531A (ja) * 1983-09-22 1985-04-17 Toshiba Corp 樹脂組成物
JPS6071631A (ja) * 1983-09-29 1985-04-23 Toshiba Corp 光硬化性組成物
JPH07189804A (ja) * 1993-12-27 1995-07-28 Toyota Motor Corp 内燃機関のピストンおよびその製造方法
JPH08217813A (ja) * 1995-02-17 1996-08-27 Toyo Ink Mfg Co Ltd 光開始剤組成物、光重合性組成物および光重合方法
JPH09143248A (ja) * 1995-11-20 1997-06-03 Toyo Ink Mfg Co Ltd 紫外線硬化型樹脂組成物およびこれを含む被覆剤
JPH11349895A (ja) * 1998-06-08 1999-12-21 Kansai Paint Co Ltd カチオン重合性塗料組成物
JP2008189853A (ja) * 2007-02-06 2008-08-21 Daicel Chem Ind Ltd 光硬化性樹脂組成物及び塗装物
JP2015185504A (ja) * 2014-03-26 2015-10-22 日立金属株式会社 エナメル線の製造方法
JP2016120476A (ja) * 2014-12-25 2016-07-07 トヨタ自動車株式会社 摺動部材およびその製造方法
JP2016121314A (ja) * 2014-12-25 2016-07-07 株式会社ダイセル 耐摩耗剤

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