JP2018176516A - Laminate, and composite molding and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate which is formed of a layer containing a polyamide-imide resin and a layer containing an epoxy resin that can be strongly adhered to the layer as a main component.SOLUTION: A laminate is formed of a first layer containing a polyamide-imide layer and a second layer being a cured product of a curable liquid composition containing an alicyclic epoxy compound represented by formula (1), where a peel strength between the first layer and the second layer by SAICAS method is 0.45 kN/m or more. In formula (1), Rto Rare each independently, H, a halogen atom, an oxo group, a hydroxyl group, a hydroperoxy group, an amino group, a sulfo group or an organic group; and X is a direct bond or linking group.SELECTED DRAWING: None

Description

  The present invention relates to a laminate for covering the surface of a molded body which is required to have slidability, heat resistance and the like, a composite molded body, and a method for producing the same.

  As a coating agent for treating the surface of various molded articles, an epoxy resin having excellent adhesion is used. In JP-A-7-189804 (Patent Document 1), a first coating layer is formed on the first coating layer after forming an abrasion resistant first coating layer containing polyamideimide or polyimide and a solid lubricant. Disclosed is a piston of an internal combustion engine having a second coating layer formed of an epoxy resin having a hardness lower than that of the layer. In this document, the first coating layer is formed of polyamideimide or polyimide in order to improve abrasion resistance as compared with a conventional epoxy resin-based single layer coating having excellent initial conformability and containing a fluorocarbon resin. There is.

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

  Japanese Patent Application Laid-Open No. 2008-189853 (Patent Document 2) is a photocurable resin that can be suitably used as a car clear paint, top coat agent for plastic film, coat agent for protecting plastic parts, coat agent for forming color filter protective film, etc. An alicyclic diepoxy compound containing a 3,4,3′4′-diepoxybicyclohexyl compound as a resin composition, an epoxy compound other than this alicyclic diepoxy compound, an oxetane compound, a vinyl ether compound, an acrylic polymer, A combination with at least one compound selected from the group consisting of 2 to 6 functional polyol compounds is disclosed.

  However, even a coating film formed of this composition has low heat resistance and does not have sufficient slidability and rigidity.

  JP-A-2014-191173 (Patent Document 3) discloses that 3,4,3'4'-diepoxybicyclohexyl, a hydroxyl group-containing silicone compound and / or a silica filler, on at least one surface of a plastic substrate. There is disclosed a hard coat film on which a hard coat layer formed of a curable composition containing an acid generator is laminated.

  However, this hard coat layer is premised to be formed on the surface of a plastic substrate, and in this document, the improvement of heat resistance is not intended.

  In particular, as compared with epoxy resins such as bisphenol A epoxy compounds used as general-purpose adhesives, alicyclic epoxy compounds are generally excellent in slidability and rigidity, but have low adhesion and adhesion. It has the characteristics. Furthermore, the slidability and the adhesion are contradictory characteristics, and it was difficult to make both characteristics compatible.

  In JP-A-60-67531 (Patent Document 4), a spiro ortho ester compound and / or spiro fluoro carbonate compound, an aluminum compound, and silanols or silanols are used as a low shrinkage resin composition having a small volume contraction rate at the time of curing. Disclosed is a composition comprising a silicon compound that produces silanol groups. In this document, epoxy compounds are described as copolymer compounds. In the example, a wire coated with an amidimide is coated with a resin composition comprising 100 g of a spiroortho ester compound, 1 g of an aluminum compound, 10 g of a silicon compound, 400 g of an epoxy compound and 5 g of a sensitizer and then the resin composition is photocured There is.

  However, this resin composition is a complex composition containing a specific compound such as a spiroorthoester compound, and has low handleability and insufficient heat resistance and abrasion resistance.

  Japanese Patent No. 5878421 (Patent Document 5) discloses a wet coating composition containing silver based particles, a polyamide based dispersant and a solvent as a composition for forming a solid lubricating layer on the surface of a sliding member by wet coating. Objects are disclosed.

  However, although the covering layer formed by this composition has high adhesion, it has low rigidity.

JP-A-7-189804 (Claim 1, Paragraph [0002] [0003], Table 1) JP 2008-189853 A (claim 1, paragraph [0014], an embodiment) Unexamined-Japanese-Patent No. 2014-191173 (Claim 1) Japanese Patent Application Laid-Open No. 60-67531 (Claim 1; Technical Field of the Invention, column 34, lines 10 to 14, Example 19) Patent No. 5878421 (Claim 1)

  Therefore, an object of the present invention is to provide a laminate capable of firmly adhering to a layer containing a polyamideimide resin and a layer coated with this laminate even if the layer is formed of a simple composition containing an epoxy resin as a main component. A composite molded body and a method of manufacturing the same.

  Another object of the present invention is to provide a laminate capable of forming a highly rigid coating with high adhesion on the surface of a molded article by coating, a composite molded article coated with this laminate, and a method for producing the same. .

  Still another object of the present invention is to provide a laminate capable of imparting slidability, heat resistance and chemical resistance to the surface of a molded article, a composite molded article coated with this laminate, and a method for producing the same. is there.

  As a result of intensive studies to achieve the above problems, the present inventors coated and cured a curable liquid composition containing a specific alicyclic epoxy compound on the first layer containing a polyamideimide resin. After that, by heating and annealing at different temperatures at which the temperature is raised in two or more steps, even a layer formed of a simple composition containing an epoxy resin as a main component, a layer containing a polyamideimide resin The inventors have found that they can be firmly adhered and complete the present invention.

  That is, the laminate of the present invention comprises a first layer containing a polyamideimide resin, and 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 hydroxyl 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)
Is a laminate with a second layer which is a cured product of a curable liquid composition containing an alicyclic epoxy compound, and the peel strength of the first layer and the second layer by the SAICAS method is 0. .45 kN / m or more. The curable liquid composition may further contain a leveling agent. It is preferable that the curable liquid composition does not contain a spiro ortho ester compound. The first layer may further contain at least one solid lubricant selected from the group consisting of a fluorine compound, a metal sulfide and a carbon material. In the above formula (1), at least one of R ^{1 to} R ¹⁸ may be a hydrogen atom, and X may be a direct bond. The indentation hardness of the second layer according to the microhardness tester may be 300 N / mm ² or more, and the elastic modulus may be 3000 N / mm ² or more.

  In the present invention, a composite molded body comprising a molded body made of metal and the laminate laminated on the molded body, and the first layer of this laminate being bonded or adhered to the molded body Also included. The metal may be aluminum alone, iron alone, nickel alone, copper alone, chromium alone, or an alloy containing any one of these alone. The composite molded body of the present invention may be a sliding member.

In the present invention, a coating step of coating a curable liquid composition for forming a second layer on the surface of a first layer laminated on the surface of a molded article made of metal, the coated curable liquid Also included is a method for producing the composite molded body, comprising a curing step of applying active energy to the composition for curing, and an annealing step of heating the composition subjected to the curing step at different temperatures obtained by raising the temperature in two or more steps. . The annealing step comprises a low temperature annealing step of heating the composition subjected to the curing step at less than 120 ° C. and a high temperature annealing step of heating the composition subjected to the low temperature annealing step at 120 ° C. or higher, and the heating time of the low temperature annealing step However, it may be longer than the heating time of the high temperature annealing process. The manufacturing method of the present invention may further include a preheating step of heating the coated curable liquid composition at 120 ° C. or less before the curing step. In the curing step, the ultraviolet light may be irradiated at an integrated light amount of 400 mJ / cm ² or more.

  In the present invention, after a curable liquid composition containing a specific alicyclic epoxy compound is coated on a first layer containing a polyamideimide resin and cured, the temperature is raised in two or more steps at different temperatures. Since it is heated and annealed, a strong network polymer structure allows firm adhesion to a layer containing a polyamideimide resin even if it is a layer formed of a simple composition containing an epoxy resin as the main component. Moreover, since it is formed of a composition containing a specific alicyclic epoxy compound and a leveling agent, a coating having high rigidity can be formed on the surface of a molded article by coating. Furthermore, slidability, heat resistance and chemical resistance can be imparted to the surface of the molded body.

[Laminate]
The laminate of the present invention is a laminate of a first layer containing a polyamideimide resin and a second layer which is a cured product of a curable liquid composition containing the alicyclic epoxy compound represented by the formula (1). It is.

(First layer)
The polyamideimide resin contained in the first layer is a polymer having an imide bond and an amide bond in the main chain, and the tricarboxylic acid anhydride (or a reactive derivative such as a halide or lower alkyl ester thereof) is reacted with a polyvalent isocyanate. The polyamidoimide which made it react, after making tricarboxylic acid anhydride and polyvalent amine react, and forming an imide bond, polyvalent isocyanate may be made to react and it may be polyamidoimide etc. which are made to react is made.

  The polyamideimide resin is usually a resin obtained by using trimellitic anhydride as the tricarboxylic acid anhydride, for example, a compound of the formula (2)

(Wherein, Y represents a group containing a divalent hydrocarbon group)
It may be a resin having a repeating unit represented by

In Y of said Formula (2), the bivalent hydrocarbon group etc. which were illustrated as X of said Formula (1) etc. are mentioned as a bivalent hydrocarbon group. The divalent hydrocarbon group may be a C _1-10 alkylene group such as ethylene group, a C _5-8 cycloalkylene group such as cyclohexylene group, etc., but from the viewpoint of heat resistance, a phenylene group or a naphthylene group And the like, preferably containing a divalent aromatic hydrocarbon group such as The 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 (eg, 1,4-phenylene group etc.) are linked via a linking group such as a thioether (sulfide) bond May be In this group, the divalent aromatic hydrocarbon group and the alkylene group are substituents (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, It may have a halogen atom such as a chlorine atom or a fluorine atom, a hydroxyl group or the like.

  As Y, for example, phenylene group (1,4-phenylene group, 1,3-phenylene group etc.), naphthylene group (1,5-naphthylene group, 2,6-naphthylene group etc.), 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 Group, etc.] or these groups are further directly bonded or the above linking group (carbonyl group, sulfonyl group, ether bond, thioether bond, etc. ) And attached group 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.

Among them, phenylene group, biphenylene group, bisphenol residue and the like are widely used, and a benzene ring (substituent group (halogen atom such as fluorine atom or chlorine atom, C _1-3 alkyl group such as methyl group, C group such as methoxy group) _The biphenylene group which may have a _1-3 alkoxy group etc. and diphenylmethane 4,4'- diyl group (bisphenol F residue) are preferable.

  The number average molecular weight of the polyamideimide resin is 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, more preferably It is about 8,000 to 100,000 (especially 10,000 to 50,000). If the molecular weight is too small, the heat resistance and mechanical properties may be reduced.

  The glass transition temperature of the polyamideimide resin may be 150 ° C. or higher, and is, for example, about 180 to 400 ° C., preferably 200 to 380 ° C., and more preferably about 250 to 350 ° C. (particularly about 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 first layer may contain a solid lubricant in addition to the polyamideimide resin. As solid lubricants, commonly used solid lubricants, for example, fluorine compounds (fluororesins such as polytetrafluoroethylene, fluorinated graphite etc.), boron compounds (boron nitride etc.), metal sulfides (eg sulfurized molybdenum disulfide etc.) Molybdenum, tungsten sulfide such as tungsten disulfide), carbon materials such as graphite (graphite, carbon black, etc.), simple metals (silver, lead, nickel, etc.), mica, organic molybdenum compounds, melamine cyanurate, etc. may be mentioned. These solid lubricants can be used alone or in combination of two or more. Among these solid lubricants, fluorine compounds (especially polytetrafluoroethylene), metal sulfides (especially molybdenum disulfide), and carbon materials (especially graphite) are preferable.

  The proportion of the solid lubricant is about 500 parts by weight or less (eg, 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 proportion of the solid lubricant is too large, the mechanical properties of the solidified coating may be degraded.

  The first layer may contain the solid lubricant in the above proportion according to the application, but it is preferable that the first layer does not contain the solid lubricant from the viewpoint of adhesion to the second layer and the molded product.

  The first layer may contain other additives as long as the heat resistance and the slidability are not impaired. Commonly used additives include curing agents (such as epoxy resins), fillers (such as inorganic fillers such as titanium oxide and alumina), stabilizers (such as antioxidants, UV absorbers, light stabilizers, heat stabilizers, etc.) ), Plasticizers, antifoaming agents, antistatic agents, flame retardants, UV absorbers, etc. may be contained. These additives may be used alone or in combination of two or more. The proportion 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 (eg, 0.01 to 30 parts by weight), preferably 10 parts by weight or less (eg, 0.1 to 10 parts by weight).

  The average thickness of the first layer may be 0.5 μm or more, and is, for example, about 0.5 to 30 μm, preferably about 1 to 20 μm, and more preferably about 3 to 15 μm (particularly about 5 to 10 μm). If the average thickness is too thin, the heat resistance and the adhesion to the first layer or the molded product may be reduced. In the present specification and the claims, the average thickness of the first layer can be measured, for example, as an average value at any 10 points using an optical film thickness meter.

(2nd layer)
The second layer is a cured product of a curable liquid composition containing the alicyclic epoxy compound represented by the formula (1).

(1) Alicyclic epoxy compound An alicyclic epoxy compound is represented by said 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.

  The organic group is not particularly limited as long as it contains a carbon atom, and examples thereof include 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 And the like.

  The hydrocarbon group includes, for example, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group.

As an aliphatic hydrocarbon group, an alkyl group, an alkenyl group, an alkynyl group is mentioned, for example. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a hexyl group, an octyl group, isooctyl group, decyl group, the C _1-20 alkyl group (preferably a dodecyl group C _{1- 10} alkyl group, more preferably a C _1-4 alkyl group) and the like. As the alkenyl group, for example, a C _2-20 alkenyl group such as a vinyl group, an allyl group, a methallyl group, a 1-propenyl group, an isopropenyl group, a butenyl group, a pentenyl group, a hexenyl group (preferably a C _2-10 alkenyl group More preferably, a _C2-4 alkenyl group etc. are mentioned. As an alkynyl group, _C2-20 alkynyl groups (Preferably _C2-10 alkynyl group, More preferably _C2-4 alkynyl group), such as an ethynyl group and propynyl group, etc. are mentioned, for example.

As the alicyclic hydrocarbon group, for example, a C _3-12 cycloalkyl group such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, _cyclododecyl group (especially C _5-8 cycloalkyl group); cyclohexenyl group C _3-12 cycloalkenyl group such as, bicycloheptadiene group, such as C _4-15 bridged cyclic hydrocarbon group such as bicyclo heptenyl group.

As an aromatic hydrocarbon group, _C6-14 aryl groups (especially _C6-10 aryl group), such as a phenyl group and a naphthyl group, etc. are mentioned, for example.

The alkoxy group is a C _1-10 alkoxy group 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) and the like. The alkenyloxy group includes, for example, 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). The aryloxy group include a phenoxy group, tolyloxy group, _{C 6-20} aryloxy group (in particular _{C 6-14} aryloxy group), such as naphthyloxy group and the like. As an aralkyloxy group, _C7-20 aralkyloxy groups (especially _C7-18 aralkyloxy group), such as a benzyloxy group and a phenethyl oxy group, etc. are mentioned, for example.

As an acyl group, _C1-20 acyl groups (especially _C1-12 acyl group), such as an acetyl group, a propionyl group, a (meth) acryloyl group, a benzoyl group, etc. are mentioned, for example. As an acyloxy group, _C1-20 acyloxy groups (especially _C1-12 acyloxy group), such as an acetyloxy group, a propionyloxy group, a (meth) acryloyloxy group, a benzoyloxy group, etc. are mentioned, for example.

The alkylthio group include a methylthio group, _{C 1-6} alkylthio groups such as ethylthio group (especially _{C 1-4} alkylthio group). The alkenylthio group, for example, _{C 2-6} alkenylthio group (especially _{C 2-4} alkenylthio group) such as allyl group and the like. As an arylthio group, _6-20 arylthio groups (especially _C6-14 arylthio group), such as a phenylthio group, a tolylthio group, a naphthylthio group, etc. are mentioned, for example. The aralkylthio group, for example, benzylthio group, _{C 6-20} aralkylthio group (especially _{C 7-18} aralkylthio group) such as phenethylthio group, and the like.

As the alkoxycarbonyl group, for example, a C _1-10 alkoxy-carbonyl group (in particular, a C _1-6 alkoxy-carbonyl group) such as a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group and the like can be mentioned. The aryloxycarbonyl group, for example, a phenoxycarbonyl group, tolyloxycarbonyl group, C _6-20 aryloxy such as naphthyloxycarbonyl group - carbonyl group (especially C _6-14 aryloxy - carbonyl group). As the aralkyloxycarbonyl group, for example, a C _7-20 aralkyloxy-carbonyl group such as a benzyloxycarbonyl group (in particular, a C _7-18 aralkyloxy-carbonyl group) and the like can be mentioned.

As an epoxy containing group, a glycidyl group, glycidyl oxy group, etc. are mentioned, for example. The oxetanyl-containing radical, such as C _1-10 alkyl oxetanyl group such as ethyloxetanyl oxy group.

Examples of the substituted amino group include mono- or dialkylamino groups such as methylamino group, ethylamino group, dimethylamino group, diethylamino group (especially mono- or di-C _1-6 alkylamino group), acetylamino group, propionylamino And an acylamino group such as benzoylamino group (in particular, a C _1-11 acylamino group).

These organic groups may be groups in which two or more types of organic groups are combined (bonded). As a combination of two or more organic groups, for example, a combination of an aliphatic hydrocarbon group and an alicyclic hydrocarbon group (such as cyclohexyl methyl group and methyl cyclohexyl group), an aliphatic hydrocarbon group and an aromatic hydrocarbon Combination with a group [C _7-18 aralkyl group such as benzyl group, phenethyl group (especially, C _7-10 aralkyl group), C _6-10 aryl-C _2-6 alkenyl group such as cinnamyl group, 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 methoxyethyl group), an aliphatic hydrocarbon group and an aryloxy Combinations with groups (such as methyl phenoxy group) and the like can be mentioned.

  The organic group may further have a substituent. As a substituent, a halogen atom, an oxo group, a hydroxyl group, a hydroperoxy group, an amino group, a sulfo group etc. are mentioned, for example.

Among them, as R ^{1 to} R ¹⁸ , a hydrogen atom, a linear or branched C _1-6 alkyl group (in particular, a linear C _1-3 alkyl group such as a methyl group) and the like are widely used, and rigidity From the point of point of view, it is preferable that at least one of R ^{1 to} R ¹⁸ be a hydrogen atom, and it is particularly preferable that all of them be a hydrogen atom.

  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 these linking groups are connected in plural. The divalent hydrocarbon group includes a divalent aliphatic hydrocarbon group, a divalent alicyclic hydrocarbon group, and a divalent aromatic hydrocarbon group.

  As a bivalent aliphatic hydrocarbon group, an alkylene group, an alkenylene group, an alkynylene group etc. are mentioned, for example.

As the alkylene group, for example, 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, dodecamethylene group and the like _{And -20} alkylene group and the like.

Examples of the alkenylene group include vinylene group, allylene group, methallyl group, 1-propenylene group, isopropenylene group, 1-butenylene group, 2-butenylene group, butadienylene group, pentenylene group, hexenylene group, octenylene group and the like C _2-20 alkenylene group etc. are mentioned. The alkenylene group may be an alkenylene group in which part or all of the carbon-carbon double bond is epoxidized.

As an alkynylene group, _C2-20 alkynylene groups, such as an ethynylene group and a propynylene group, etc. are mentioned, for example.

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, bicycloheptenylene group, etc. may be mentioned. 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 epoxy cyclohexylene group.

As a bivalent aromatic hydrocarbon group, _C6-14 arylene groups, such as a phenylene group and a naphthylene group, etc. are mentioned, for example.

These divalent hydrocarbon groups may have a substituent. As the substituent, for example, in addition to the substituents exemplified as the substituents of the organic group in R ^{1 to} R ¹⁸ , C _1-4 alkyl groups such as methyl group and ethyl group, C such as methoxy group and ethoxy group _{A 1-4} alkoxy group, a carbonyl group, etc. are mentioned.

  These linking groups may be (combined or linked) groups combining two or more linking groups. As a combination of two or more types of linking groups, for example, a combination of a divalent aliphatic hydrocarbon group and a divalent alicyclic hydrocarbon group (eg, cyclohexylmethylene group, methylenecyclohexylene group, dicyclohexylmethane) -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, tolylene group, xylylene group) , A diphenylmethane-4,4'-diyl group, a diphenylpropane-4,4'-diyl group, etc., a combination of an ester bond and a divalent hydrocarbon group (eg, a carbonyloxy methylene group, a carbonyloxy hydrogenated xylylene group) (Eg, an oxycarbonyl group), a combination of a carbonate bond and a divalent hydrocarbon group (eg, methylene oxycarbony) A combination of multiple ester bonds (eg, a polyester bond such as polycaprolactone etc.), a combination of a plurality of ether bonds (eg, polyoxyethylene ethylene glycol, methylene oxy carbonyl oxyhydrogenated xylylene oxy carbonyl oxy methylene group, etc.) Groups, etc.), combinations of plural ether bonds and plural ester bonds (polyether ester bonds), combinations of plural urethane bonds (polyurethane bonds), a combination of epoxy cycloalkylene groups and polyester bonds, etc. Can be mentioned.

Among these, as X, a direct bond, an alkylene group (a 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 (eg, a C _1-4 alkyleneoxy C _1-4 alkylene group such as a methylene oxymethylene group), a combination of an ester bond and an alkylene group (eg, a carbonyloxy C ₁ such as a carbonyloxy methylene 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.

Multiple The alicyclic epoxy compound represented by the formula (1) may include only the alicyclic epoxy compound of a single species, the type of the substituents R ¹ to R ¹⁸ and / or group X are different It may be a combination of various cycloaliphatic epoxy compounds.

Preferred alicyclic epoxy compounds include, for example, methyl groups such as 3,4,3 ′, 4′-diepoxybicyclohexyl, (3,4,3 ′, 4′-diepoxy-6-methyl) bicyclohexyl, etc. Diepoxybi C _5-8 cycloalkyl optionally having 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 Alkane carboxylate etc. are mentioned. These alicyclic epoxy compounds can be used alone or in combination of two or more.

(2) Curing Agent The curable liquid composition preferably further contains a curing agent. As a curing agent, a cationic polymerization initiator (acid generator) or a conventional curing agent [eg, acid and acid anhydride curing agents, amine curing agents, polyaminoamide curing agents, imidazole curing agents, organic acid hydrazides Curing agents, latent curing agents (such as dicyandiamides), polymercaptan curing agents, phenolic curing agents and the like] and the like.

  Among 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 sulfonium salts (salts of sulfonium ions and anions), iodonium salts (salts of iodonium ions and anions), selenium salts (salts of selenium ions and anions), ammonium salts (ammonium ions) And salts of phosphonium ions (salts of phosphonium ions and anions), salts of transition metal complex ions and anions, and the like. These photoacid generators can be used alone or in combination of two or more. Among these photoacid generators, an acid generator having a high acidity, for example, a sulfonium salt is preferable in that the reactivity can be improved and the hardness of the cured product can be improved.

  As the sulfonium salt, for example, triphenylsulfonium salt, tri-p-tolylsulfonium salt, tri-o-tolylsulfonium salt, tris (4-methoxyphenyl) sulfonium salt, 1-naphthyldiphenylsulfonium salt, 2-naphthyldiphenylsulfonium Salts, tris (4-fluorophenyl) sulfonium salt, tri-1-naphthylsulfonium salt, tri-2-naphthylsulfonium salt, tris (4-hydroxyphenyl) sulfonium salt, diphenyl [4- (phenylthio) phenyl] sulfonium salt, Triarylsulfonium salts such as [4- (4-biphenylthio) phenyl] -4-biphenylphenylsulfonium salt, 4- (p-tolylthio) phenyl di- (p-phenyl) sulfonium salt; diphenylphenacylsulfo Diarylsulfonium salts such as sodium salts, diphenyl 4-nitrophenacylsulfonium salts, diphenylbenzylsulfonium salts, diphenylmethylsulfonium salts; phenylmethylbenzylsulfonium salts, 4-hydroxyphenylmethylbenzylsulfonium salts, 4-methoxyphenylmethylbenzylsulfonium salts And 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.

As an anion (counter ion) for forming a salt with a cation, for example, 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- and the} like], (C ₆ F ₅ ) ₄ B ⁻ , (C ₆ F ₅ ) ₄ Ga ⁻ , sulfonate anion (trifluoromethanesulfonate anion, pentafluoroethanesulfonate anion) Nonafluorobutanesulfonic acid anion, methanesulfonic acid anion, benzenesulfonic acid anion, p-toluenesulfonic acid anion, etc., (CF ₃ SO ₂ ) ₃ C ⁻ , (CF ₃ SO ₂ ) ₂ N ⁻ , perhalogenated acid Ion, halogenated sulfonate ion, sulfate ion, carbonate ion, aluminate ion, hexafluorobisma Examples thereof include a sulfate ion, a carboxylate ion, an aryl borate ion, a thiocyanate ion, and a nitrate ion. Among these anions, fluorinated alkyl fluorophosphate ions are preferred from the viewpoint of solubility and the like.

  A photo-acid generator can use a commercially available photo-acid generator. Examples of commercially available photoacid generators include “CPI-101A”, “CPI-110A”, “CPI-100P”, “CPI-110P”, “CPI-210S”, and “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, boron trifluoride amine complexes and the like. These thermal acid generators can be used alone or in combination of two or more. Among these thermal acid generators, acid generators having high acidity, such as arylsulfonium salts, are preferable in that they can improve the reactivity and the hardness of the cured product. As an anion, the anion similar to a photo-acid generator etc. is mentioned, The fluoride ion of antimony, such as SbF ^6- etc., may be sufficient.

  A thermal acid generator can also use a commercially available thermal acid generator. Examples of commercially available thermal acid generators include “San Aid SI-60L”, “San Aid SI-60 S”, “San Aid SI-80 L”, “San Aid SI-100 L”, manufactured by Sanshin Chemical Industry Co., Ltd. ) "SP-66" and "SP-77" manufactured by ADEKA can be used.

  Examples of amine-based curing agents include aliphatic polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenediamine, diethylaminopropylamine, hexamethylenediamine, polypropylenetriamine, and the like; mensenediamine, isophoronediamine, bis (4-amino-3-methyldicyclohexyl) methane, diaminodicyclohexylmethane, bis (aminomethyl) cyclohexane, N-aminoethylpiperazine, 3,9-bis (3-aminopropyl) -3,4,8,10-tetra Alicyclic 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-naphthylenediamine And aromatic polyamines such as 2,6-naphthylenedamine. 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 (mensenediamine, isophorone diamine, etc.), aromatic polyamines (xylenediamine) And metaphenylene diamine etc.).

  Among these, cationic polymerization initiators (acid generators) are preferable from the viewpoint of promoting polymerization and improving the hardness of the cured product.

  The proportion of the curing agent can be selected from the 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 according to 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 with respect to 100 parts by weight of the alicyclic epoxy compound, and for example, 0.05 to 5 parts by weight, preferably 0.1 to 3 parts by weight Part, more preferably about 0.3 to 2 parts by weight (especially 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 reduced. If it is too large, the storage stability of the composition may be reduced or the cured product may be colored. There is a risk.

  The proportion of a conventional curing agent such as an amine 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.

(3) Leveling Agent The curable liquid composition preferably further contains a leveling agent. Any leveling agent may be used as long as it has a surface tension reducing ability, and a conventional leveling agent (such as ethylene oxide adduct of acetylene glycol) can be used, but from the viewpoint of excellent surface tension reducing ability, a silicone based leveling agent Fluorine-based leveling agents are preferred. In the present invention, by combining the alicyclic epoxy compound and the leveling agent, the surface smoothness can be improved and the slidability can be improved. Furthermore, by using a specific leveling agent, not only the hardness can be maintained, but also the hardness can be improved by controlling the blending ratio.

The silicone-based leveling agent may be any leveling agent having a polyorganosiloxane skeleton. As a polyorganosiloxane skeleton, a monofunctional M unit (generally represented by R ₃ SiO _1/2 ), a difunctional D unit (generally represented by R ₂ SiO _2/2 ) Units), trifunctional T units (generally represented by RSiO _3/2 ), and tetrafunctional Q units (generally represented by SiO _4/2 ) Any siloxane may be used, but usually a polyorganosiloxane formed of D units is used. The organic group (R) of the polyorganosiloxane can be selected from the hydrocarbon groups exemplified as R ^{1 to} R ¹⁸ of the formula (1) of the alicyclic epoxy compound, but usually a C _1-4 alkyl. A group or an aryl group is used, and a methyl group or a phenyl group (especially a methyl group) is generally used. The repeating number (degree of polymerization) of the siloxane unit is, for example, about 2 to 3,000, preferably about 3 to 2,000, and more preferably about 5 to 1,000.

The fluorine-based leveling agent may be any leveling agent having a fluoroaliphatic hydrocarbon skeleton. As a fluoro aliphatic hydrocarbon skeleton, for example, fluoro C _1-10 alkanes such as fluoromethane, fluoroethane, fluoropropane, fluoroisopropane, fluorobutane, fluoroisobutane, fluoro t-butane, fluoropentane, fluorohexane and the like It can be mentioned.

  In these fluoroaliphatic hydrocarbon backbones, at least a part of hydrogen atoms may be substituted with fluorine atoms, but all hydrogen atoms are substituted with fluorine atoms in terms of improving the slidability and rigidity. Perfluoroaliphatic hydrocarbon backbones are preferred.

Furthermore, the fluoroaliphatic hydrocarbon backbone may form a polyfluoroalkylene ether backbone which 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 _{fluoroC 1-4} alkylene groups such as fluoromethylene group, fluoroethylene group, fluoropropylene group and fluoroisopropylene group, It is also good. These fluoroaliphatic hydrocarbon groups may be the same or may be a combination of two or more. The repeating number (degree of polymerization) of the fluoroalkylene ether unit may be, for example, about 10 to 3,000, preferably about 30 to 1,000, and more preferably about 50 to 500.

  Among these skeletons, a polyorganosiloxane skeleton is preferable from the viewpoint of being excellent in affinity with the cation curable silicone resin.

  A leveling agent having such a skeleton has a hydrolytic condensation group, a functional group such as a reactive group to an epoxy group, a radical polymerizable group, a polyether group, a polyester group, etc., to impart various functionalities. It may have a polyurethane group or the like. Further, the silicone-based leveling agent may have a fluoroaliphatic hydrocarbon group, and the fluorine-based leveling agent may have a polyorganosiloxane group.

The hydrolytic condensation group includes, for example, a hydroxysilyl group; a trihalosilyl group such as a trichlorosilyl group; a dihalo C _1-4 alkylsilyl group such as a dichloromethylsilyl group; a dihaloaryl silyl group such as a dichlorophenylsilyl group; Haroji C _1-4 alkylsilyl group such as Kuroroji C _1-4 alkylsilyl such as silyl group; trimethoxysilyl group, tri C _1-4 alkoxysilyl group such as triethoxysilyl group; dimethoxymethylsilyl group, diethoxymethyl Di C _1-4 alkoxy C _1-4 alkyl silyl group such as silyl group; Di C _1-4 alkoxy aryl silyl group such as dimethoxyphenyl silyl group, diethoxyphenyl silyl group; methoxy dimethyl silyl group, ethoxy dimethyl silyl group etc _{C 1-4} alkoxy C _1-4 alkylsilyl group; methoxydiphenylsilyl, _{C 1-4} alkoxy diarylsilyl group such as ethoxy diphenyl silyl; methoxymethylphenyl silyl group, _{C 1-4} alkoxy _{C 1-4} alkyl aryl, such as ethoxymethyl triphenylsilyl group A silyl group etc. are mentioned. Among these, tri-C _1-4 alkoxysilyl groups such as trimethoxysilyl group are preferable in terms of reactivity and the like.

  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, from the viewpoint of reactivity and the like, a hydroxyl group, an amino group, an acid anhydride group, an isocyanate group and the like are widely used, and a hydroxyl group is preferable from the viewpoint of handleability and availability.

  As a radically polymerizable group, a (meth) acryloyloxy group, a vinyl group etc. are mentioned, for example. Among these, (meth) acryloyloxy group is widely used.

As a polyether group, polyoxy _C2-4 alkylene groups, such as a polyoxyethylene group, a polyoxypropylene group, a polyoxybutylene group, a polyoxyethylene polyoxypropylene group, etc. are mentioned, for example. In the polyether group, the repeating number (additional mole number) of the oxyalkylene group is, for example, about 2 to 1000, preferably about 3 to 100, and more preferably about 5 to 50. Of these, polyoxy C _2-3 alkylene group such as a polyoxyethylene group or a polyoxypropylene group (especially polyoxyethylene group) are preferred.

  As a polyester group, for example, a polyester group formed by the reaction of a dicarboxylic acid (an aromatic carboxylic acid such as terephthalic acid or an aliphatic carboxylic acid such as adipic acid) with a diol (an aliphatic diol such as ethylene glycol) And polyester groups formed by ring-opening polymerization of cyclic esters (eg, lactones such as caprolactone).

  As a polyurethane group, a conventional polyester type polyurethane group, a polyether type polyurethane group etc. are mentioned, for example.

  These functional groups may be introduced as a direct bond to the polyorganosiloxane skeleton or fluoroaliphatic hydrocarbon skeleton, and a linking group (eg, an alkylene group, a cycloalkylene group, an ether bond, an ester bond, It may be introduced via an amide bond, a urethane bond, or a linking group combining these.

  Among these functional groups, from the viewpoint of being able to react with an alicyclic epoxy compound and improve the hardness of a cured product, a reactive group for a hydrolytic condensation group or an epoxy group is preferable, and a reactive group for an epoxy group ( Particularly preferred is a hydroxyl group).

The hydroxyl group may be a terminal hydroxyl group of a (poly) oxyalkylene group [such as (poly) oxyethylene group]. As such a leveling agent, for example, a silicone-based 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 Fluorinated leveling agent (fluoroalkylpolyoxyethylene) 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 Etc.).

  A commercially available silicone type leveling agent can be used as a silicone type leveling agent. As a commercially available silicone type | system | group leveling agent, the leveling agent ("BYK-300", "BYK-301 / 302", "BYK-306", "BYK-307", the BYK series made by BIC Chemie Japan KK), for example, "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-UV 3500 "," BYK-UV3 10 "," BYK-UV 3570 "," BYK-3550 "," BYK-SILCLEAN 3700 "," BYK-SILCLEAN 3720 ", etc., Algin Chemie AC series leveling agent (" AC FS 180 "," AC FS 360 "," AC S20 ", etc.), Kyoeisha Chemical Co., Ltd. Polyflow series leveling agent (" 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 agent (" KP-323 "," KP-326 "," KP-341 "," KP-104 ", "KP-110", "KP-112", etc.) Leveling agent ("LP-7001", "LP-7002", "8032 ADDITIVE", "57 ADDITIVE", "L-7604", "FZ-2110", "FZ-2105", "67 ADDITIVE", Examples include "8618 ADDITIVE", "3 ADDITIVE", "56 ADDITIVE", and the like.

  A commercially available fluorine-type leveling agent can be used as a fluorine-type leveling agent. As commercially available fluorine-based leveling agents, for example, leveling agents ("DSX", "DAC-HP") manufactured by Daikin Industries, Ltd. manufactured by Daikin Industries, Ltd., and leveling agents manufactured by AGC Seimi Chemical Co., Ltd. manufactured by Surfron series (" "S-242", "S-243", "S-420", "S-611", "S-651", "S-386", etc., BYK series BYK series leveling agent "BYK-340", etc.) Algin Chemie AC series leveling agent ("AC 110a", "AC 100a" etc.), DIC Corporation's Megafuck series leveling agent ("Megafuck F-114", "Megafuck F-410", "Megafuck F-444", "Megafuck EXP TP 2066", "MegaFat F-430 "," Megafuck F-472SF "," Megafuck F-477 "," Megafuck F-552 "," Megafuck F-553 "," Megafuck F-554 "," Megafuck F- " 555 "," Megafuck R-94 "," Megafuck RS-72-K "," Megafuck RS-75 "," Megafuck F-556 "," Megafuck EXP TF-1367 "," Megafuck EXP " TF-1437 "," Megafuck F-558 "," Megafuck EXP TF-1537 ", etc., Sumitomo 3M Co., Ltd. FC series leveling agent (" FC-4430 "," FC-4432 ", etc.), Ltd. NEOS HOTTERgent Series Leveling Agents ("FURTAGENT 100", "FURTAGENT 100C", "FURTAGE" 110, "Futagent 150", "Futagent 150 CH", "Futagent A-K", "Futagent 501", "Futagent 250", "Futagent 251", "Futagent 222F", "Futagent" GENT 208 G "," FURTAGENT 300 "," FURTAGENT 310 "," FURTgent 400 SW, etc. ", Kitamura Chemical Industries, Ltd. PF series leveling agent (" PF-136A "," PF-156A "," PF-Series ") PF-151N "," PF-636 "," PF-6320 "," PF-656 "," PF-6520 "," PF-651 "," PF-652 "," PF-3320 ", etc. It can be mentioned.

  These leveling agents can be used alone or in combination of two or more kinds. For example, plural kinds of silicone type leveling agents and plural kinds of fluorine type leveling agents may be respectively combined, and the silicone type leveling agent and the fluorine type leveling agent And may be used in combination. Among these leveling agents, a silicone-based leveling agent having a hydroxyl group is preferable from the viewpoint of being excellent in affinity with the alicyclic epoxy compound, capable of reacting with the epoxy group, and improving the hardness and appearance of the cured product.

  As a silicone type leveling agent which has a hydroxyl group, for example, polyether modified polyorganosiloxane which introduce | transduced the polyether group into the principal chain or side chain of polyorganosiloxane frame | skeleton (polydimethylsiloxane etc.), the principal chain of polyorganosiloxane frame | skeleton Or polyester modified polyorganosiloxane which introduce | transduced polyester group into the side chain, silicone modified (meth) acrylic resin which introduce | transduced polyorganosiloxane into (meth) acrylic resin, etc. are mentioned. In these leveling agents, the hydroxyl group may have a polyorganosiloxane skeleton, or may have a polyether group, a polyester group, or a (meth) acryloyl group. As such a leveling agent, "BYK-370", "BYK-SILCLEAN 3700", "BYK-SILCLEAN 3720" etc. made by Big Chemie Japan KK can be used, for example.

  The proportion 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 proportion of the leveling agent is too small, the slidability of the cured product may be reduced, and if too large, the hardness of the cured product may be reduced.

  In particular, the proportion of the silicone-based 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. It may be about part (especially 0.5 to 2 parts by weight). The proportion of the fluorine-based leveling agent is, for example, 0.05 to 5 parts by weight, preferably 0.1 to 3 parts by weight, and more preferably 0.2 to 1 parts by weight, per 100 parts by weight of the alicyclic epoxy compound. In particular, it may be about 0.3 to 0.8 parts by weight. When the proportion of the leveling agent is adjusted to 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 considered as a function of the leveling agent, can be improved.

(4) Other Additives The curable liquid composition may contain other 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 from the viewpoint of reactivity and miscibility. As another epoxy resin, a glycidyl ether type epoxy resin, a glycidyl ester type epoxy resin, a glycidyl amine type epoxy resin, a long chain aliphatic epoxy resin etc. can be illustrated, for example. The proportion of the other curable resin is about 100 parts by weight or less, for example 50 parts by weight or less (eg, 1 to 50 parts by weight), preferably 30 parts by weight or less (eg, 30 parts by weight or less). 5 to 30 parts by weight).

  The curable liquid composition may contain conventional additives as long as the slidability and rigidity are not impaired. Conventional additives include, for example, curing accelerators (imidazoles, alkali metal or alkaline earth metal alkoxides, phosphines, amide compounds, Lewis acid complex compounds, sulfur compounds, boron compounds, condensable organic metal compounds, etc.) Fillers (Inorganic fillers such as titanium oxide and alumina), Stabilizers (antioxidants, UV absorbers, light stabilizers, heat stabilizers etc), plasticizers, lubricants, antifoams, antistatic agents, You may contain a flame retardant, an ultraviolet absorber, etc. These additives may be used alone or in combination of two or more. The total proportion of these additives is about 100 parts by weight or less, for example, 30 parts by weight or less (eg, 0.01 to 30 parts by weight), preferably 10 parts by weight or less, per 100 parts by weight of the alicyclic epoxy compound. (For example, 0.1 to 10 parts by weight) or so.

  Furthermore, the curable liquid composition may contain an organic solvent or water. Examples of the organic solvent include 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.), alcohols (ethanol, isopropanol, butanol, cyclohexanol etc.), Cellosolves (methyl cellosolve, ethyl cellosolve, etc.), cellosolve acetates, amides (dimethylformamide, dimethylacetamide, etc.) and the like can be mentioned. These solvents can be used alone or in combination of two or more.

  The solid content weight of the curable liquid composition can be optionally selected and not particularly limited in order to adjust to the viscosity of the liquid composition suitable for the process depending on the process of the molding process.

(5) Properties of Second Layer The second layer is formed of a simple composition containing the above-mentioned alicyclic epoxy compound as a main component, and the spiroorthoester compound and spiroorthocarbonate described in Patent Document 4 Even if it does not contain the compound, the adhesion to the first layer can be improved. Therefore, it is preferable that the second layer does not contain the spiroorthoester compound and the spiroorthocarbonate compound (in particular, the spiroorthoester compound).

  In the present invention, the adhesion between the first layer and the second layer can be evaluated by SAICAS (Surface And Interfacial Cutting Analysis System; surface / interface physical property analysis device or surface / interface cutting test device) method. Specifically, the peel strength between the first layer and the second layer according to the SAICAS method may be 0.45 kN / m or more, and for example, 0.45 to 1 kN / m, preferably 0.5 to 0.951 kN. / M, more preferably about 0.6 to 0.9 kN / m (particularly about 0.65 to 0.8 kN / m). If the peel strength is too low, the adhesion between the first layer and the second layer may not be sufficient. In the present specification and the claims, the peel strength according to the SAICAS method can be measured, for example, using the method described in the example of surgery.

The second layer, high hardness, indentation hardness by microhardness meter may be 300N / mm ² or more (e.g. 300~1000N / mm ^2), preferably 350 N / mm ² or more (e.g. 350～800N / mm ^2), it is more preferably 400 N / mm ² or more (e.g. 400~700N / mm ² approximately). The second layer may have an elastic modulus of 3,000 N / mm ² or more (eg, 3,000 to 10,000 N / mm ² ) according to a microhardness tester, preferably 4,000 N / mm ² or more (eg, 4,000 to 8,000 N / mm ² ), Preferably, it is 5000 N / mm ² or more (for example, about 5000 to 6000 N / mm ² ). If the indentation hardness and the elastic modulus are too small, it may be difficult to maintain the wear resistance of the second layer for a long time. In the present specification and claims, the indentation hardness and the elastic modulus can be measured, for example, using a microhardness tester ("ENT-2100" manufactured by Elionix Co., Ltd.).

  The arithmetic average roughness Ra of the second layer may be 100 nm or less (eg, 1 to 100 nm), for example, 2 to 50 nm, preferably 3 to 30 nm (eg, 4 to 20 nm), more preferably 5 to 15 nm (particularly 7) (About 10 nm). In the present invention, the combination of the second layer containing the alicyclic epoxy compound (especially an alicyclic epoxy compound in which X is a direct bond) represented by the above (1) and the first layer containing a polyamideimide resin 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 mean roughness Ra is too large, the surface smoothness may be reduced, which may lead to a decrease in the slidability. In the present specification and claims, the average roughness can be measured by a method in accordance with JIS B0601 (2001).

  The average thickness of the second layer can be selected according to the type of molded article covered by the laminate, but may be, for example, 12 μm or more (particularly 15 μm or more), for example 12 to 100 μm, preferably 15 to 50 μm, and further Preferably, it is about 20 to 40 μm (especially 22 to 35 μm). In the present specification and claims, the average thickness of the second layer can also be measured as an average value at any 10 points using, for example, an optical film thickness meter.

[Composite molded body]
The composite molded body of the present invention includes a molded body formed of metal and the laminate laminated on the molded body, and the first layer of the laminate is joined or adhered to the molded body. . The first layer of the laminate is excellent not only in the adhesion to the second layer but also in the adhesion to the molded product, and can be bonded to the molded product without an intervening adhesive layer. The first layer may be a primer layer for the molded article, and the second layer may be a top coat layer (uppermost layer).

  The molded body can be used as a surface treatment agent for coating various molded bodies (two-dimensional or three-dimensional molded bodies), and is not particularly limited, but it is excellent in slidability and heat resistance. It may be a transport member such as a car or aircraft, or a sliding member such as electronic and electrical equipment (for example, a sliding member such as a cylinder, a piston, or a bearing).

  It does not specifically limit as a metal which comprises a molded object, According to the kind of molded object, what is necessary is just the metal utilized conventionally. As a metal, aluminum, iron, nickel, copper, chromium etc. are mentioned, for example. The metal may be the metal alone or an alloy of the metal (for example, stainless steel, steel, etc.). Furthermore, the metal surface may be subjected to plating treatment such as zinc plating for anti-corrosion treatment. Among these, metals including aluminum and iron are widely used, and in the case of a sliding member such as a piston, they are usually formed of a metal including aluminum (such as aluminum alone or an aluminum alloy). The alloy containing aluminum may be, for example, an alloy of aluminum and a metal such as silicon, copper, or magnesium.

[Method of producing composite molded body]
The composite molded article of the present invention comprises a coating step of coating a curable liquid composition for forming a second layer on the surface of a first layer formed on the surface of a molded article made of metal, and coated. The hardening process which gives active energy to a curable liquid composition and is hardened, and the annealing process which heats the composition which passed through the hardening process at the different temperature which raised temperature by two or more steps.

(Coating process)
In the coating step, as a coating method, conventional methods such as roll coating, air knife coating, blade coating, rod coating, reverse coating, bar coating, comma coating, die coating, gravure coating, screen coating method, spray method, Spinner method etc. are mentioned. Among these methods, blade coating method, bar coating method, gravure coating method, spray method and the like are widely used.

(Preheating process)
The curable liquid composition may undergo a preheating step of heating and drying (preheating) the coated curable liquid composition prior to the curing step. In the present invention, the adhesion between the first layer and the second layer can be improved and the rigidity of the second layer can also be improved through the preheating step. The preheating temperature can be selected from the range of 150 ° C. or less (particularly 120 ° C. or less), for example, 40 to 120 ° C., preferably 50 to 110 ° C., more preferably 60 to 100 ° C. (especially 70 to 90 ° C.) It is. The preheating time is about 10 seconds or more (eg, 10 seconds to 10 minutes), preferably 20 seconds or more (eg, 20 seconds to 5 minutes), and more preferably 30 seconds or more (eg, 30 seconds to 2 minutes). Good.

(Curing process)
In the curing step, the curable liquid composition may be cured by applying active energy, depending on the type of curing agent. As active energy, for example, heat and / or light energy rays can be used, and in particular, light irradiation using light energy rays is useful. As the light energy ray, radiation (gamma ray, X-ray, etc.), ultraviolet ray, visible ray, electron beam (EB), etc. can be used, and usually, ultraviolet ray, electron beam is often used. In particular, in applications where polymerization can be performed without using a curing agent and high weather resistance is required, electron beam irradiation may be performed.

As a light source, for example, in the case of ultraviolet light, 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, excimer laser) etc. may be used it can. Integrated light quantity (light quantity or radiation energy) varies depending on the thickness of the coating film, for example 50~10000mJ / cm ^2, preferably 70~5000mJ / cm ^2, even more preferably from 100~1000mJ / cm ² of about Good. Furthermore, the laminated light amount may be 400 mJ / cm ² or more, for example, 400 to 3000 mJ / cm, in that the adhesion between the first layer and the second layer can be improved, and the rigidity of the second layer can be improved. ² , preferably about 500 to 2000 mJ / cm ² , more preferably about 600 to 1000 mJ / cm ² . The illuminance is, for example, about 10 to 100 mW / cm ² , preferably about 20 to 80 mW / cm ² , and more preferably about 30 to 70 mW / cm ² (particularly about 40 to 60 mW / cm ² ).

  In the case of the electron beam, a method of irradiating the electron beam by an exposure source such as an electron beam irradiation device can be used. The irradiation dose (dose) varies depending on the thickness of the coating, but is, for example, about 1 to 200 kGy (gray), preferably about 5 to 150 kGy, and more preferably about 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 of a light energy beam (in particular, an electron beam) may be performed in an inert gas (for example, nitrogen gas, argon gas, helium gas, etc.) atmosphere, if necessary.

  On the other hand, in the case of heat curing 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 step, a curing treatment using active energy rays such as ultraviolet rays is preferable in that it can be used for a wide range of molded products.

(Annealing process)
In the present invention, the composition having undergone the curing step is heated at different temperatures obtained by raising the temperature in two or more steps to form a stronger network polymer structure, and the first layer and the second layer are formed. In addition to improving adhesion, the rigidity of the second layer can also be improved. The heat treatment may be carried out by raising the temperature in two or more steps, but from the viewpoint of productivity etc., for example, it may be heated in 2 to 4 steps, preferably 2 to 3 steps, more preferably 2 steps .

  When heating in two steps, the annealing step (or the aging step) comprises a low temperature annealing step of heating the composition that has undergone the curing step and a high temperature annealing step of heating at a temperature higher than the heating temperature of the low temperature annealing step The temperature difference between the heating temperature in the low temperature annealing step and the heating temperature in the high temperature annealing step may be 10 ° C. or more, for example 10 to 150 ° C., preferably 30 to 120 ° C., more preferably 50 to 100 ° C. ~ 90 ° C). If the temperature difference is too small, the effect of the two-step annealing may not be exhibited.

  Specifically, the heating temperature in the low temperature annealing step may be less than 120 ° C., for example, 30 to 115 ° C., preferably 50 to 110 ° C., more preferably 60 to 100 ° C. (particularly 70 to 90 ° C.) It is. If the heating temperature in the low temperature annealing step is too high, the adhesion between the first layer and the second layer and the rigidity of the second layer may be reduced.

  The heating temperature in the high temperature annealing step may be 120 ° C. or higher, and is, for example, about 120 to 250 ° C., preferably about 125 to 220 ° C., and more preferably about 130 to 200 ° C. (particularly about 140 to 160 ° C.). If the heating temperature in the high temperature annealing step is too low, curing may be insufficient and the mechanical strength of the second layer may be reduced.

  The heating time of the low temperature annealing step is preferably longer than the heating time of the high temperature annealing step. The heating time of the low temperature annealing process may be 1.1 times or more of the heating time of the high temperature annealing process, for example, 1.2 to 10 times, preferably 1.5 to 5 times, more preferably 2 to 4 times (Especially 2.5 to 3.5 times). If the heating time of the low temperature annealing process is too short, the effect of the two-stage annealing process may not be exhibited.

  Specifically, the heating time of the low temperature annealing step may be 10 minutes or more, for example, 10 minutes to 20 hours, preferably 30 minutes to 10 hours, and more preferably 1 to 5 hours (particularly 2.5 to 5 hours). 3.5 hours). If the heating time of the low temperature annealing step is too short, the molecular weight of the cured product main chain may be reduced, and the adhesion between the first layer and the second layer and the rigidity of the second layer may be reduced.

  The heating time of the high temperature annealing step may be 5 hours or less, for example, 5 minutes to 5 hours, preferably 10 minutes to 3 hours, more preferably 30 minutes to 2 hours (particularly 45 minutes to 1.5 hours) It is an extent. If the heating time of the high temperature annealing step is too long, there is a possibility that the mechanical strength of the second layer may be reduced due to the heating damage.

  The annealing step is particularly effective when light energy rays (especially ultraviolet rays) are irradiated as active energy in the curing step.

(First layer formation process)
The first layer formation step for forming the first layer is not particularly limited, and a conventional method can be used, and for example, a method of solidifying a liquid composition containing a polyamideimide resin may be used.

The liquid composition may contain, in addition to the polyamideimide resin, an organic solvent and water. As the organic solvent, for example, amides (eg, N-mono or di C _1-4 alkylformamide such as N-methylformamide, N, N-dimethylformamide, etc .; N-methylacetamide, N, N-dimethylacetamide etc. N-mono or di C _1-4 alkyl acetamide; N-methyl pyrrolidone etc., ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone etc.), ethers (dioxane, tetrahydrofuran etc.), aliphatic hydrocarbons (hexane Etc.), alicyclic hydrocarbons (eg cyclohexane), aromatic hydrocarbons (eg benzene, toluene), halogenated carbons (eg dichloromethane, dichloroethane etc.), esters (eg methyl acetate, ethyl acetate), alcohols (Methanol, Ethane , 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. Among these solvents, preferred solvents for polyamideimide resins such as N-methylpyrrolidone are preferred.

  The solid content weight of the liquid composition can be optionally selected in order to adjust the viscosity of the liquid composition suitable for the process according to the process of the molding process, and is not particularly limited. You can choose from the range of

  As a method of coating the liquid composition, the same method as the method of coating the curable liquid composition for forming the second layer can be used.

  The method for solidifying the liquid composition is not particularly limited, and may be natural drying or heat drying, but firing treatment is preferable from the viewpoint of improving the strength of the first layer and the adhesion to the formed product.

  The firing temperature may be 120 ° C. or higher, and is, for example, about 120 to 300 ° C., preferably about 150 to 280 ° C., and more preferably about 160 to 250 ° C. (particularly about 180 to 230 ° C.). If the firing temperature is too low, the strength of the first layer and the adhesion to the formed product may be reduced. The baking time is about 1 minute or more (eg, 1 minute to 3 hours), preferably about 10 minutes or more (eg, 10 minutes to 2 hours), and more preferably about 30 minutes or more (eg, 30 minutes to 1.5 hours).

  The baking treatment for forming the first layer may be a heat treatment (for example, the annealing step) for forming the second layer in the second layer forming step, in which case the second layer is The annealing treatment for forming also serves as the baking treatment of the first layer. From the viewpoint of being able to improve the surface smoothness of the second layer, the baking treatment for forming the first layer is preferably performed not in the second layer forming step but in the first layer forming step.

  The present invention will be described in more detail based on examples given below, but the present invention is not limited by these examples. In addition, the detail of the raw material and sliding member which were used by the Example and the comparative example is as follows, and it evaluated by the method shown below about the composite molded object (hardened film) obtained by the Example and the comparative example.

[material]
(Raw material for the first layer)
Polyamide imide: "Morikote D-7409" manufactured by Toray Dow Corning Co., Ltd.
(Raw material for the second layer)
Alicyclic epoxy compound: 3,4,3 ′, 4′-diepoxybicyclohexyl curing agent: [4- (4-biphenylthio) phenyl] -4-biphenylphenylsulfonium tris (pentafluoroethyl) trifluorophosphate leveling Agent: Polyether modified polydimethyl siloxane solution having a hydroxyl group, "BYK-SILCLEAN 3720" manufactured by Big Chemie Japan Co., Ltd.

[Film thickness]
The thickness of the first layer and the second layer was measured using a dual type film thickness meter ("LZ-990" manufactured by Ketto Scientific Research Institute Co., Ltd.).

[SAICAS]
It measured on condition of the following using the surface and interface cutting test device ("DN-GS" by Daiprawintess Co., Ltd. product).

Measurement mode: Low-speed mode Cutting blade: Borazon cutting blade (blade width 1 mm, squee angle 20 °, niger angle 10 °)
Vertical displacement measurement point: Cutting blade support Horizontal speed: 2 μm / sec
Vertical velocity: 0.1 μm / sec
Cut limit: Manual (ON when reaching the interface between the first layer and the second layer).

[Indentation hardness, elastic modulus, elastic plastic ratio]
Using a microhardness tester ("ENT-2100" manufactured by Elionix Co., Ltd.), measurement was performed under the following conditions to determine an average value (n = 9).

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

[Curing degree]
It evaluated on the following conditions using the differential scanning calorimeter ("DSC-Q2000" by TA Instruments company), and evaluated the curing degree relatively from the exothermic peak which appears in the vicinity of 220 degreeC.

Atmosphere: Nitrogen Temperature range: 0 to 320 ° C (1st heat only)
Temperature rising rate: 10 ° C./min.

Comparative Example 1
After applying polyamide imide as a primer layer (first layer) on an aluminum plate (ADC 12 flat plate) degreased with acetone using a hand spray gun ("W-101" manufactured by Anest Iwata Co., Ltd.), Baking was performed at 200 ° C. for 120 minutes.

On the obtained primer layer, a hand spray gun (Anest Iwata (stock) as a top coat layer (second layer), 100 parts by weight of an alicyclic epoxy compound, 0.25 parts by weight of a curing agent and 1 part by weight of a leveling agent ) After spray coating using “W-101” made in the above, followed by irradiation with ultraviolet light at a conveyor speed of 1.0 m / min using a conveyor type ultraviolet curing apparatus (“Aicure” manufactured by Panasonic Corporation) It was treated with a metal halide lamp (output 70%, illuminance 50 mW / cm ² ) and ultraviolet light with an integrated light amount of 800 mJ / cm ² to prepare a composite molded body (coated aluminum plate) having a primer layer and a top coat layer. The average thickness of the coating (total thickness of the primer layer and the top coat layer) was 30 μm.

Comparative example 2
After forming a primer layer (first layer) in the same manner as in Comparative Example 1, 100 parts by weight of an alicyclic epoxy compound, 0.25 parts by weight of a curing agent and leveling are formed thereon as a top coat layer (second layer) 1 part by weight of the agent was spray-coated using a hand spray gun ("W-101" manufactured by Anest Iwata Co., Ltd.) and curing was attempted by heat treatment (high temperature annealing treatment) at 150.degree. C. for 1 hour It did not cure.

Comparative example 3
After applying polyamide imide as a primer layer (first layer) on an aluminum plate (ADC 12 flat plate) degreased with acetone using a hand spray gun ("W-101" manufactured by Anest Iwata Co., Ltd.), Baking was performed at 200 ° C. for 120 minutes.

On the obtained primer layer, a hand spray gun (Anest Iwata (stock) as a top coat layer (second layer), 100 parts by weight of an alicyclic epoxy compound, 0.25 parts by weight of a curing agent and 1 part by weight of a leveling agent After spray coating using “W-101” manufactured in Japan), prebaking is performed at 80 ° C. for 1 minute, and then, using a conveyor type ultraviolet curing apparatus (“Aicure” manufactured by Panasonic Corporation), the conveyor speed is 1.0 m It was irradiated with ultraviolet light at a rate of 1 minute and treated with a metal halide lamp (output 70%, illuminance 50 mW / cm ² ) and ultraviolet light with an integrated light amount of 800 mJ / cm ² . Finally, the coated film of the top coat layer was cured by heat treatment (high temperature annealing treatment) at 150 ° C. for 1 hour to prepare a composite molded body (coated aluminum plate) having a primer layer and a top coat layer. The average thickness of the coating (the total thickness of the primer layer and the top coat layer) was 34 μm.

Example 1
After applying polyamide imide as a primer layer (first layer) on an aluminum plate (ADC 12 flat plate) degreased with acetone using a hand spray gun ("W-101" manufactured by Anest Iwata Co., Ltd.), Baking was performed at 200 ° C. for 120 minutes.

On the obtained primer layer, a hand spray gun (Anest Iwata (stock) as a top coat layer (second layer), 100 parts by weight of an alicyclic epoxy compound, 0.25 parts by weight of a curing agent and 1 part by weight of a leveling agent ) After spray coating using “W-101” made in the above, followed by irradiation with ultraviolet light at a conveyor speed of 1.0 m / min using a conveyor type ultraviolet curing apparatus (“Aicure” manufactured by Panasonic Corporation) It was treated with a metal halide lamp (output 70%, illuminance 50 mW / cm ² ) and ultraviolet light with an integrated light amount of 400 mJ / cm ² . Finally, the top coat layer is cured by heat treatment (low temperature annealing treatment) at 80 ° C. for 5 hours and then heat treatment (high temperature annealing treatment) at 150 ° C. for 1 hour to form the primer layer and the top coat layer. A composite molded body (painted aluminum plate) was produced. The average thickness of the coating (the total thickness of the primer layer and the top coat layer) was 32 μm.

Examples 2 to 12
A composite molded body was produced in the same manner as in Example 1 except that the conditions shown in Table 1 were changed.

  The evaluation results of the composite molded body obtained in Examples and Comparative Examples are shown in Table 1.

  As is clear from the results in Table 1, the composite molded articles obtained in the examples have high peel strength and high rigidity of the second layer.

  The degree of cure of Comparative Example 3 and Example 8 was evaluated. The approximate values of the exothermic peaks observed at around 220 ° C. are 44 J / g and 23 J / g, respectively, and Example 8 annealed at two stages of low temperature and high temperature has a small exothermic peak and a high degree of cure (Comparative Example 3 0.5 times). Annealing in two steps results in a stronger network polymer structure, higher peel strength and higher rigidity of the second layer.

The composite molded article of the present invention is a variety of molded articles (two-dimensional or three-dimensional molded articles) formed of a metal that is required to have slidability and heat resistance, for example, various industrial devices, transport machines such as automobiles and aircrafts. , Electronic and electrical devices (e.g., sliding members such as cylinders, pistons, bearings, etc.).

Claims (13)

A first layer containing a polyamideimide resin, and 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 hydroxyl 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)
Is a laminate with a second layer which is a cured product of a curable liquid composition containing an alicyclic epoxy compound, and the peel strength of the first layer and the second layer by the SAICAS method is 0. A laminate having a .45 kN / m or more.   The laminate according to claim 1, wherein the curable liquid composition further comprises a leveling agent.   The laminate according to claim 1 or 2, wherein the curable liquid composition does not contain a spiro ortho ester compound.   The laminate according to any one of claims 1 to 3, wherein the first layer further comprises at least one solid lubricant selected from the group consisting of a fluorine compound, a metal sulfide and a carbon material. The laminate according to any one of claims 1 to 4, wherein in the formula (1), at least one of R ^{1 to} R ¹⁸ is a hydrogen atom, and X is a direct bond. The laminate according to any one of claims 1 to 5, wherein the indentation hardness of the second layer by a microhardness tester is 300 N / mm ² or more, and the elastic modulus is 3000 N / mm ² or more.   A molded body formed of metal and the laminate according to any one of claims 1 to 6 laminated on the molded body, and the first layer of the laminate is joined or adhered to the molded body Composite molded body.   The composite molded body according to claim 7, wherein the metal is an aluminum simple substance, an iron simple substance, a nickel simple substance, a copper simple substance, a chromium simple substance or an alloy containing any of these single substances.   The composite molded body according to claim 7, which is a sliding member.   Coating step of coating a curable liquid composition for forming a second layer on the surface of a first layer laminated on the surface of a molded article made of metal, active energy of the coated curable liquid composition The composite formed body according to any one of claims 7 to 9, comprising: a curing step of applying and curing, and an annealing step of heating the composition subjected to the curing step at different temperatures obtained by raising the temperature in two or more steps. Production method.   The annealing step comprises a low temperature annealing step of heating the composition subjected to the curing step at less than 120 ° C. and a high temperature annealing step of heating the composition subjected to the low temperature annealing step at 120 ° C. or higher The manufacturing method according to claim 10, wherein the heating time of the high temperature annealing step is longer.   12. The method according to claim 10, further comprising a preheating step of heating the coated curable liquid composition at 120 ° C. or less before the curing step. In the curing step, the manufacturing method according to any one of claims 10 to 12 is irradiated with ultraviolet rays in integrated light intensity 400 mJ / cm ² or more.