WO2017081963A1 - Surface treatment kit as well as composite molded article and method for producing same - Google Patents

Abstract

Treating the surface of a metal molded article by using a surface treatment kit that includes a curable liquid composition (A) containing an alicyclic epoxy compound represented by formula (1) and a liquid composition (B) containing a polyamide-imide resin makes it possible to impart slidability and heat resistance to the surface of the molded article. (In the formula, R¹-R¹⁸ are the same or different and represent a hydrogen atom, halogen atom, oxo group, hydroxy group, hydroperoxy group, amino group, sulfo group, or organic group; and X represents a direct bond or a linking group)

Description

Surface treatment kit, composite molded body, and method for producing the same

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. In JP-A-7-189804 (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. In this document, 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.

However, this document does not describe details of the epoxy resin, and general-purpose epoxy resins have low slidability and rigidity (hardness).

Japanese Patent Application Laid-Open No. 2008-189853 (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. As 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.

However, even a coating film formed from this composition has low heat resistance and insufficient sliding properties and rigidity.

Japanese Patent Application Laid-Open No. 2014-191173 (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.

However, it is assumed that this hard coat layer is formed on the surface of a plastic substrate, and this document does not intend to improve heat resistance.

In particular, compared with epoxy resins such as bisphenol A-type epoxy compounds that are used as general-purpose adhesives, 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)

Therefore, 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.

As a result of intensive studies to achieve the above-mentioned problems, 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. By processing, it discovered that slidability and heat resistance could be provided to the surface of a molded object, and completed this invention.

That is, 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)

(Wherein 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. In the formula (1), 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. In addition, 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).

In the present invention, since 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.

[Curable liquid composition (A)]
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.

(Alicyclic epoxy compound)
The alicyclic epoxy compound is represented by the formula (1). In R ¹ to R ¹⁸ of 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.

Examples of the hydrocarbon group 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). Examples of the alkenyl group 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). Examples of the alkynyl group 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.

Examples of the aromatic hydrocarbon group include C _6-14 aryl groups (particularly C _6-10 aryl groups) such as a phenyl group and a naphthyl group.

Examples of the alkoxy group 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). Group). Examples of the alkenyloxy group 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). Examples of the aryloxy group 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. Examples of the aralkyloxy group include a C _7-20 aralkyloxy group (particularly a C _7-18 aralkyloxy group) such as a benzyloxy group and a phenethyloxy group.

Examples of the acyl group include C _1-20 acyl groups such as acetyl group, propionyl group, (meth) acryloyl group, and benzoyl group (particularly, C _1-12 acyl group). Examples of the acyloxy group include C _1-20 acyloxy groups such as acetyloxy group, propionyloxy group, (meth) acryloyloxy group, and benzoyloxy group (particularly, C _1-12 acyloxy group).

Examples of the alkylthio group include a C _1-6 alkylthio group such as a methylthio group and an ethylthio group (particularly a C _1-4 alkylthio group). Examples of the alkenylthio group include a C _2-6 alkenylthio group such as an allylthio group (particularly a C _2-4 alkenylthio group). Examples of the arylthio group include _6-20 arylthio groups (particularly C _6-14 arylthio groups) such as a phenylthio group, a tolylthio group, and a naphthylthio group. Examples of the aralkylthio group include a C _6-20 aralkylthio group (particularly a C _7-18 aralkylthio group) such as a benzylthio group and a phenethylthio group.

Examples of the alkoxycarbonyl group 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). Examples of the aryloxycarbonyl group 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). Examples of the aralkyloxycarbonyl group 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.

Examples of the substituted amino group 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. And acylamino groups such as benzoylamino group (particularly C _1-11 acylamino group).

These organic groups may be groups in which two or more organic groups are combined (bonded). Examples of 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. C _1-4 alkyl-substituted aryl group, C _2-4 alkenyl-substituted aryl group such as styryl group], a combination of an alkoxy group and an aliphatic hydrocarbon group (such as a methoxyethyl group), an aliphatic hydrocarbon group and aryloxy A combination with a group (such as a methylphenoxy group) may be mentioned.

The organic group may further have a substituent. Examples of the substituent include a halogen atom, an oxo group, a hydroxy group, a hydroperoxy group, an amino group, and a sulfo group.

Among these, as 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 In view of the above, at least one of R ¹ to R ¹⁸ is preferably a hydrogen atom, and all of them are particularly preferably hydrogen atoms.

In X, 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.

Examples of the divalent aliphatic hydrocarbon group include an alkylene group, an alkenylene group, and an alkynylene group.

Examples of the alkylene group 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.

Examples of the alkenylene group 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.

Examples of the alkynylene group include C _2-20 alkynylene groups such as ethynylene group and propynylene group.

Examples of the divalent alicyclic hydrocarbon group 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.

Examples of the divalent aromatic hydrocarbon group include a C _6-14 arylene group such as a phenylene group and a naphthylene group.

These divalent hydrocarbon groups may have a substituent. Examples of the substituent 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. Examples include _1-4 alkoxy groups and carbonyl groups.

These linking groups may be groups in which two or more linking groups are combined (bonded or connected). As 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). -4,4'-diyl group, dicyclohexylpropane-4,4'-diyl group, etc.), 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 polycaprolactone), a combination of a plurality of ether bonds (for example, polyoxyethylene) Polyether bonds such as groups), combinations of multiple ether bonds and multiple ester bonds (polyether ester bonds), combinations of multiple urethane bonds (polyurethane bonds), combinations of epoxy cycloalkylene groups and polyester bonds, etc. Is mentioned.

Among these, as 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) _-4 etc. 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 Epoxy C _5-8 cycloalkyl C _1-4 alkyl (epoxy) C _5-8 cyclo _optionally having a C _1-4 alkyl group such as methyl (3,4-epoxy-6-methyl) cyclohexanecarboxylate Examples include alkane carboxylates. These alicyclic epoxy compounds can be used alone or in combination of two or more.

(Curing agent)
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.].

Of these, 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.

Examples of the photoacid generator 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. Of these photoacid generators, 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.

Examples of the sulfonium salt include triphenylsulfonium salt, tri-p-tolylsulfonium salt, tri-o-tolylsulfonium salt, tris (4-methoxyphenyl) sulfonium salt, 1-naphthyldiphenylsulfonium salt, and 2-naphthyldiphenylsulfonium salt. 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-hydroxyphenylmethylbenzylsulfonium salt, 4-methoxyphenylmethylbenzylsulfonium salt Monoarylsulfonium salts such as dimethylphenacylsulfonium salts, phenacyltetrahydrothiophenium salts, and trialkylsulfonium salts such as dimethylbenzylsulfonium salts. These sulfonium salts can be used alone or in combination of two or more. Of these sulfonium salts, triarylsulfonium salts are preferred.

Examples of the anion (counter ion) for forming a salt with the cation 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 sulfonate ion, sulfate ion, carbonate ion, aluminate ion, hexafluorobismer Examples thereof include oxalate ion, carboxylate ion, arylborate ion, thiocyanate ion, and nitrate ion. Of these anions, fluorinated alkyl fluorophosphate ions are preferred from the viewpoint of solubility.

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.

Examples of the thermal acid generator 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. Examples of the anion include the same anions as those of the photoacid generator, and may be an antimony fluoride ion such as SbF ^6- .

A commercially available thermal acid generator can also be used as the thermal acid generator. Examples of commercially available 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.

Examples of the amine curing agent 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-diamine, 3,5-diethyltolylene-2,4-diamine, 3,5-diethyltolylene-2,6-diamine, biphenylenediamine, 4,4-diaminodiphenylmethane, 2,5-naphthylene diene Examples thereof include aromatic polyamines such as amines and 2,6-naphthylenediamine. These amine curing agents can be used alone or in combination of two or more. Among these, aliphatic polyamines (ethylenediamine, diethylenetriamine, triethylenediamine, tetraethylenepentamine, diethylaminopropylamine, hexamethylenediamine, etc.), alicyclic polyamines (mensendiamine, isophoronediamine, etc.), aromatic polyamines (xylenediamine) , Metaphenylenediamine, etc.) are widely used.

Of these, cationic polymerization initiators (acid generators) 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. Examples of 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.

In these 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.

Furthermore, 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.

Of these skeletons, 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.

Examples of 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 Nirushiriru, C _1-4 alkoxy diarylsilyl group such as ethoxy diphenyl silyl; methoxymethylphenyl silyl group, such as C _1-4 alkoxy C _1-4 alkyl aryl silyl groups such as ethoxymethyl triphenylsilyl group. Of these, a tri C _1-4 alkoxysilyl group such as a trimethoxysilyl group is preferable from the viewpoint of reactivity.

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. Among these, 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.

Examples of the radical polymerizable group include a (meth) acryloyloxy group and a vinyl group. Of these, (meth) acryloyloxy groups are widely used.

Examples of the polyether group include polyoxy C _2-4 alkylene groups such as a polyoxyethylene group, a polyoxypropylene group, a polyoxybutylene group, and a polyoxyethylene-polyoxypropylene group. In the polyether group, the number of repeating oxyalkylene groups (number of added moles) is, for example, about 2 to 1000, preferably about 3 to 100, and more preferably about 5 to 50. Of these, polyoxyC _2-3 alkylene groups such as polyoxyethylene groups and polyoxypropylene groups (particularly polyoxyethylene groups) are preferred.

Examples of the polyester group 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). And polyester groups formed by ring-opening polymerization of cyclic esters (for example, lactones such as caprolactone).

Examples of the polyurethane group 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).

Among these functional groups, 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]. As such 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 ”,“ BYK-UV3570 ”,“ BYK-3550 ”,“ BYK-SILCLEAN3700 ”,“ BYK-SILCLEAN3720 ”, etc.), Algin Chemie AC series leveling agents (“ AC FS180 ”,“ AC FS360 ”,“ AC S20 etc.), Kyoeisha Chemical Co., Ltd. polyflow series leveling agents ("Polyflow KL-400X", "Polyflow KL-400HF", "Polyflow KL-401", "Polyflow KL-402", "Polyflow KL") -403 "," Polyflow KL-404 ", etc.), Shin-Etsu Chemical Co., Ltd. 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. Examples of 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. "BYK-340", etc.), Algin Chemie AC series leveling agents ("AC 110a", "AC 100a", etc.), DIC Corporation mega fuck series leveling agents ("Megafac F-114", “Megafuck F-410”, “Megafuck F-444”, “Megafuck EXP TP-2066”, “Megafa Ku-F-430, Mega-F-F-472SF, Mega-F-F-477, Mega-F-F-552, Mega-F-F-553, Mega-F-F-554, Mega-F -555 "," Megafuck R-94 "," Megafuck RS-72-K "," Megafuck RS-75 "," Megafuck F-556 "," Megafuck EXP TF-1367 "," Megafuck " EXP TF-1437 "," Megafac F-558 "," Megafac EXP TF-1537 ", etc.) Sumitomo 3M FC series leveling agents (" FC-4430 "," FC-4432 ", etc.) , Leveling agents from Neos Corporation, “Factent 100”, “Factent 100C”, “Cover” "Factent 110", "Factent 150", "Factent 150CH", "Factent AK", "Factent 501", "Factent 250", "Factent 251", "Factent 222F", "Footer Gent 208G "," Furgent 300 "," Furgent 310 "," Furgent 400SW ", etc.), Kitamura Chemical Industry Co., Ltd. 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.

These leveling agents can be used alone or in combination of two or more. For example, 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. Among these leveling agents, 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.

Examples of the silicone-based leveling agent having a hydroxyl group 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. Or the polyester modified polyorganosiloxane which introduce | transduced the polyester group into the side chain, the silicone modified (meth) acrylic resin which introduce | transduced the polyorganosiloxane to the (meth) acrylic resin, etc. are mentioned. In these leveling agents, the hydroxyl group may have a polyorganosiloxane skeleton, or a polyether group, a polyester group, or a (meth) acryloyl group. As such 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.

In particular, 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). When the ratio of the leveling agent is adjusted within these ranges, not only the slidability of the cured product can be improved, but also the hardness of the cured product, which has not been conventionally assumed as a function of the leveling agent, can be improved.

(Other additives)
The curable liquid composition (A) may contain another curable resin. Examples of other 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. Examples of 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).

Further, 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.). , 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.

[Liquid composition (B)]
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)

(In the formula, Y represents a group containing a divalent hydrocarbon group)
The resin which has a repeating unit represented by these may be sufficient.

In Y of the formula (2), 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. It is preferable to contain a divalent aromatic hydrocarbon group such as 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 carbonyl group; a sulfonyl group; an ether bond; a group in which a plurality of divalent aromatic hydrocarbon groups (for example, 1,4-phenylene group) are bonded via a linking group such as a thioether (sulfide) bond. May be. In this group, 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, sulfonyl group, ether bond, thioether bond). Etc.) and bonded groups through, the substituent on the benzene ring of these groups include groups in substituted. These groups can be used alone or in combination of two or more.

Of these, 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. _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.

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).

The liquid composition (B) may contain a solid lubricant in addition to the polyamideimide resin. Examples of 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. These solid lubricants can be used alone or in combination of two or more. Of these solid lubricants, fluorine compounds (particularly polytetrafluoroethylene), metal sulfides (particularly molybdenum disulfide), and carbon materials (particularly graphite) are preferred.

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).

Furthermore, 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.), water, alcohol (Methanol, ethanol, isopropanol, butanol, cyclohexanol, etc.), cellosolves (methyl cellosolve, ethyl cellosolve, etc.), may contain such cellosolve acetates. These solvents can be used alone or in combination of two or more. Of these solvents, good solvents for polyamideimide resins such as N-methylpyrrolidone are preferred.

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%.

[Laminated body and composite molded body]
In the present invention, 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. Although it may be used as an agent, from the viewpoint that the slidability can be further improved, a first layer (a heat-resistant layer or a primer layer) containing a polyamideimide resin and 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). In the present invention, 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). Therefore, high surface smoothness with an arithmetic average roughness Ra of 20 nm or less (particularly 10 nm or less) can also be realized. If the arithmetic average roughness Ra is too large, the surface smoothness may be reduced, leading to a decrease in slidability.

The average thickness of the first layer may be, for example, 0.5 μm or more, for example, 0.5 to 30 μm, preferably 0.8 to 10 μm, and more preferably 1 to 5 μm (especially 1.5 to 3 μm). 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 μm or more, for example, 1 to 100 μm, preferably 5 to 80 μm, and more preferably about 10 to 50 μm. If the second layer is too thin, the slidability and rigidity may be reduced.

In the present invention, 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 | cures the said curable liquid composition (A).

In the first layer forming step, 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. Examples include coating, screen coating method, spray method, spinner method and the like. Among these methods, 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.).

In the present invention, 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).

In addition, 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.

In the second layer forming step, as the coating method of the curable liquid composition (A), 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.

In the second layer forming step, 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.

In the curing treatment, 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. In particular, in applications where polymerization can be performed without using a curing agent and high weather resistance is required, irradiation with an electron beam may be performed.

As the light source, 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 (irradiation energy) 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. Furthermore, in order to improve the adhesion to the two-dimensional or three-dimensional shaped body, 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.

In the case of an electron beam, 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 (especially electron beams) may be performed in an inert gas (for example, nitrogen gas, argon gas, helium gas, etc.) atmosphere if necessary.

In addition, after hardening with an active energy ray, you may heat-process (annealing process or aging process) the 2nd layer after hardening. In the aging treatment, 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.

On the other hand, when thermosetting is performed using a thermal cationic polymerization initiator, 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.

As the curing treatment, a curing treatment using active energy rays such as ultraviolet rays is preferable because it can be used for a wide range of supports.

In the present invention, 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). Furthermore, the metal surface may be subjected to plating treatment such as galvanization for rust prevention treatment. Among these, metals containing aluminum and iron are widely used, and metals containing aluminum (such as aluminum alone or aluminum alloys) are preferable.

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. In addition, the detail of the raw material used by the Example and the comparative example is as follows, The laminated body obtained by the Example and the comparative example was evaluated by the following items.

[material]
(Resin for top coat layer)
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.
(Additive)
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”.

[Film thickness]
The thickness of the coating film coated and cured on the aluminum plate was measured using a dual type film thickness meter ("LZ-990" manufactured by Ketto Scientific Laboratory).

[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.

[Boiling water resistance]
Dip a coated aluminum plate (composite molded product) with a clip in a SUS beaker containing purified water, heat it with a hot plate, boil for 5 hours, and then visually and cross-cut the condition of the painted surface. did.

[Scratch test]
The durability and adhesion of the coating film coated on the aluminum plate by the scratch test were evaluated. Using a Macro Mechanical Tester (manufactured by NANOVEEA), a linear scratch test was performed at a load load speed of 50 N / min and a scratch speed of 10 mm / min within a load range of 0.3 N to 50 N. The deformation start load and the peel load were evaluated.

[Indentation hardness]
Using a micro hardness tester (“ENT-2100” manufactured by Elionix Co., Ltd.), measurement was performed under the following conditions to obtain an average value (n = 9).

Measurement mode: Load-unload mode Surface detection: Inclination (2.0)
Load curve: 5 mN (linear) over 10 seconds
Creep: 5mN for 10 seconds
Unloading curve: 0 mN (linear) over 10 seconds
Indenter: Berkovic indenter.

[Smoothness]
Arithmetic average roughness Ra was measured based on JIS B0601 (2001) using a fine shape measuring instrument ("ET4000A" manufactured by Kosaka Laboratory Ltd.).

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.

On the obtained primer layer, as a top coat layer (second 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. After that, 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 . 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 a primer layer and a topcoat layer was produced. The average thickness of the coating film (total thickness of the primer layer and the topcoat layer) was 37 μm.

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 μm.

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.

On the obtained primer layer, as a top coat layer (second 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. After that, 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 . Finally, after heat treatment at 150 ° C. for 1 hour as an aging treatment, 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 (total thickness of the primer layer and the topcoat layer) was 31 μm.

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 μm.

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 μm.

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 μm.

Comparative Example 1
On the aluminum plate degreased with acetone, 100 parts by weight of alicyclic epoxy compound A and 0.25 parts by weight of a curing agent were applied as a top coat layer using wire bar # 20, and then prebaked at 80 ° C. for 1 minute. Subsequently, using a belt conveyor type high-pressure mercury lamp (“UVC-02516S1” manufactured by Ushio Electric Co., Ltd.), ultraviolet light is irradiated at a conveyor speed of 5.5 m / min with a 120 W lamp output, and an integrated light quantity of 400 mJ / cm ^2. Treated with UV light. 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 29 μm.

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 μm.

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 μm.

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 μm.

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 μm.

Comparative Example 6
On the aluminum plate degreased with acetone, an acrylic oligomer was applied as a primer layer (first layer) using a wire bar # 3, prebaked at 80 ° C. for 1 minute, and then a belt conveyor type high-pressure mercury lamp ( Using UVO-02516S1 manufactured by Ushio Electric Co., Ltd., ultraviolet rays were irradiated at an output of 80 W at a conveyor speed of 6.7 m / min and treated with ultraviolet rays having an integrated light quantity of 200 mJ / cm ² .

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 μm.

Table 1 shows the results of evaluating the composite molded bodies obtained in Examples and Comparative Examples.

As is clear from the results in Table 1, the composite molded bodies of the examples had high adhesion and heat resistance, and had excellent surface smoothness. In contrast, 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, and 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).

Claims (13)

1. A surface treatment kit for treating a surface of a molded body formed of a metal, comprising a formula (1)
   

   

   (Wherein 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 surface treatment kit containing the curable liquid composition (A) containing the alicyclic epoxy compound represented by these, and the liquid composition (B) containing a polyamideimide resin.
2. The surface treatment kit according to claim 1, wherein the curable liquid composition (A) further comprises a curing agent.
3. The surface treatment kit according to claim 1 or 2, wherein the curable liquid composition (A) further comprises a leveling agent.
4. The surface treatment kit according to any one of claims 1 to 3, wherein the liquid composition (B) further contains at least one solid lubricant selected from the group consisting of a fluorine compound, a metal sulfide and a carbon material.
5. The surface treatment kit according to any one of claims 1 to 4, wherein in formula (1), at least one of R ¹ to R ¹⁸ is a hydrogen atom, and X is a direct bond.
6. A laminate having a first layer containing a polyamideimide resin and a second layer containing a cured product of the curable liquid composition (A) according to claim 1.
7. The laminate according to claim 6, wherein the indentation hardness by the microhardness meter of the second layer is 300 N / mm ² or more.
8. The laminate according to claim 6 or 7, wherein the arithmetic average roughness Ra of the surface of the second layer is 1 to 100 nm.
9. The laminate according to any one of claims 6 to 8, wherein the average thickness of the second layer is 2 to 100 times the average thickness of the first layer.
10. A molded body formed of a metal and the laminated body according to any one of claims 6 to 9 laminated on the molded body, and the first layer of the laminated body is bonded or adhered to the molded body. Composite molded body.
11. The composite molded body according to claim 10, wherein the metal is an aluminum simple substance or an alloy containing aluminum.
12. The composite molded body according to claim 10 or 11, which is a sliding member.
13. The first layer forming step of coating and solidifying the liquid composition (B) on the surface of the molded body formed of metal, and coating the curable liquid composition (A) on the surface of the obtained first layer. The method for producing a composite molded body according to any one of claims 10 to 12, further comprising a second layer forming step of curing.