JP2011218333A - Method of forming multilayer coating film and coated article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of forming a multilayer coating film having excellent adhesiveness to a base material, particularly a plastic material and having remarkably excellent weather resistance and scuff resistance and to provide a coated article having the multilayer coating film.SOLUTION: The method of forming the multilayer coating film includes steps for: forming an undercoating film using an ordinary temperature-setting or thermosetting undercoating material composition (I) on a base material; and then, forming a topcoating film using an activated energy ray curing type topcoating material composition (II) containing a silsesquioxane compound (a) which has organic groups each directly bonded to a silicon atom and in which at least one of the organic groups directly bonded to the silicon atom is an organic group having an urethane bond and one (metha)acryloyloxy group and a photopolymerization initiator (b) thereon.

Description

  The present invention relates to a method for forming a multilayer coating film capable of forming a multilayer coating film excellent in adhesion to a substrate, particularly a plastic material, and having excellent weather resistance and scratch resistance, and the multilayer coating film. It relates to the coated article which has.

  Plastic materials such as polymethyl methacrylate resin, polystyrene resin, and polycarbonate resin are excellent in impact resistance, transparency, light weight, and easy to process. Used in windows, lamp lenses, and instrument covers. However, since plastic materials are inferior to glass in terms of surface properties such as scratch resistance, chemical resistance, and weather resistance, the surface properties of plastic materials have been improved. As methods for improving the surface properties of plastic materials, methods for applying polyorganosiloxane-based and melamine-based thermosetting coating compositions and methods for applying polyfunctional acrylate-based active energy ray-curable coating compositions have been proposed. ing.

  In connection with these methods, Patent Documents 1 and 2 disclose poly (meth) acrylates of mono- or polypentaerythritol, urethane (meth) acrylates having at least two (meth) acryloyl groups in the molecule, and poly (meth) acrylates. An invention relating to a coating composition obtained by blending [(meth) acryloyloxyalkyl] (iso) cyanurate in a specific ratio is disclosed. This coating composition is excellent in scratch resistance and weather resistance.

  On the other hand, as a method for improving the scratch resistance and weather resistance of a general coating composition, there is a method of blending an inorganic material or an inorganic-organic hybrid material in the coating composition. For example, Patent Documents 3 and 4 disclose a phyllosilicate mineral type composed of a 2: 1 type or 1: 1 type laminate of a tetrahedral sheet having silicon as a central atom and an octahedral sheet having a metal as a central atom. And a layered silicon polymer having an organic group covalently bonded to at least a part of silicon. Patent Document 5 describes a coating composition using the layered silicon polymer described in Patent Documents 3 and 4 as a filler.

  In recent years, as the use of synthetic resins outdoors increases, further improvements in the surface properties (scratch resistance, weather resistance) of plastic materials are required. However, the coating composition described in Patent Document 5 cannot provide a coating composition that forms a cured film having excellent scratch resistance, weather resistance, and adhesion to a plastic substrate that satisfies the above requirements. Further, even when the layered silicon polymer described in Patent Documents 3 and 4 is blended with the coating composition described in Patent Documents 1 and 2, excellent scratch resistance, weather resistance, and adhesion to a plastic substrate satisfying the above requirements. The coating composition which forms the cured film which has the property cannot be obtained.

  Moreover, in order to eliminate the malfunction of the 1 coat coating film by the above coating compositions, the patent document 6 has proposed the multilayer coating film formation method using a specific undercoat. However, in the method described in Patent Document 6, the composition of the top coat is mainly composed of organic components, and weather resistance and scratch resistance compared to the composition containing the inorganic materials and inorganic-organic hybrid materials described in Patent Documents 3 to 5 above. There was a problem that the property was insufficient.

Japanese Patent Laid-Open No. 5-230397 JP-A-6-128502 JP-A-6-200034 JP-A-7-126396 JP-A-8-12899 JP 2006-263616 A

  The present invention has been made in view of the above circumstances, and an object of the present invention is a multilayer coating film that is excellent in adhesion to a substrate, particularly a plastic material, and very excellent in weather resistance and scratch resistance. Is a multilayer coating film forming method, and a coated article having the multilayer coating film.

  As a result of intensive studies to solve the above problems, the present inventors have solved the above problems by using an active energy ray-curable top coat composition containing a specific silsesquioxane compound and a photopolymerization initiator. The inventors have found that this can be solved, and have completed the present invention.

  That is, the present invention has an organic group bonded directly to a silicon atom on an undercoating film formed on a substrate using a room temperature curing or thermosetting undercoating composition (I). A silsesquioxane compound (a), wherein at least one of the organic groups directly bonded to the silicon atom is an organic group having a urethane bond and one (meth) acryloyloxy group, and A multi-layer coating film forming method characterized by forming a top coating film using an active energy ray-curable top coating composition (II) containing a photopolymerization initiator (b), and formed by the method The present invention relates to a coated article having a multilayer coating film.

  ADVANTAGE OF THE INVENTION According to this invention, the multilayer coating film excellent in abrasion resistance, a weather resistance, and the adhesiveness with respect to a base material can be obtained by using a specific active energy ray hardening-type top coat composition. Moreover, the coated article which has this multilayer coating film can be obtained.

  The room temperature curing or thermosetting undercoating composition (I) used in the present invention is not particularly limited as long as it can be dried / cured at room temperature, or can be cured by heating, and conventionally known room temperature curing or heat. A curable coating composition can be used. In particular, when the substrate is a plastic, those containing an acrylic resin, an ultraviolet absorber, and a light stabilizer can be suitably used from the viewpoint of ensuring weather resistance.

  As the above-mentioned acrylic resin, conventionally known ones can be used without limitation. For example, the acrylic resin may contain at least one crosslinkable functional group such as a hydroxyl group, a carboxyl group, an alkoxysilyl group, and an epoxy group. Those obtained by copolymerizing a polymerizable unsaturated monomer mixture can be suitably used.

  Examples of the polymerizable unsaturated monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl ( (Meth) acrylate, tert-butyl (meth) acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, tridecyl (meth) acrylate, lauryl ( (Meth) acrylate, stearyl (meth) acrylate, “isostearyl acrylate” (trade name, manufactured by Osaka Organic Chemical Industry Co., Ltd.), cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, t-butylcyclohexyl (meta) Alkyl or cycloalkyl (meth) acrylate such as acrylate, cyclododecyl (meth) acrylate; polymerizable unsaturated monomer having an isobornyl group such as isobornyl (meth) acrylate; an adamantyl group such as adamantyl (meth) acrylate Polymerizable unsaturated monomer: vinyl aromatic compounds such as styrene, α-methylstyrene, vinyltoluene; vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, γ- (meth) acryloyloxypropyl Polymerizable unsaturated monomers having alkoxysilyl groups such as trimethoxysilane and γ- (meth) acryloyloxypropyltriethoxysilane; perfluorobutylethyl (meth) acrylate, perfluorooctylethyl Perfluoroalkyl (meth) acrylates such as meth) acrylate; polymerizable unsaturated monomers having a fluorinated alkyl group such as fluoroolefin; polymerizable unsaturated monomers having a photopolymerizable functional group such as maleimide group; N-vinylpyrrolidone , Ethylene, butadiene, chloroprene, vinyl propionate, vinyl acetate and other vinyl compounds; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxy Ε of monoesterified product of (meth) acrylic acid such as butyl (meth) acrylate and dihydric alcohol having 2 to 8 carbon atoms, monoesterified product of (meth) acrylic acid and dihydric alcohol having 2 to 8 carbon atoms -Caprolactone modified product, N-hydroxymethyl (me ) Hydroxyl group-containing polymerizable unsaturated monomers such as acrylamide, allyl alcohol and polyoxyethylene (meth) acrylate; Carboxyl group-containing polymerizable unsaturated monomers such as (meth) acrylic acid, maleic acid, crotonic acid and β-carboxyethyl acrylate Including (meth) acrylonitrile, (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylamide, adducts of glycidyl (meth) acrylate and amines, etc. Nitrogen polymerizable unsaturated monomer; polymerizable unsaturated monomer having two or more polymerizable unsaturated groups in one molecule such as allyl (meth) acrylate and 1,6-hexanediol di (meth) acrylate; Glycidyl (meth) acrylate, β-methylglycidyl (meth) Epoxy group-containing polymerizable unsaturated compounds such as acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxycyclohexylethyl (meth) acrylate, 3,4-epoxycyclohexylpropyl (meth) acrylate, and allyl glycidyl ether Monomer; (Meth) acrylate having a polyoxyethylene chain whose molecular end is an alkoxy group; 2-acrylamido-2-methylpropanesulfonic acid, allylsulfonic acid, styrenesulfonic acid sodium salt, sulfoethyl methacrylate, and its sodium salt and ammonium Polymerizable unsaturated monomers having a sulfonic acid group such as a salt; 2-acryloyloxyethyl acid phosphate, 2-methacryloyloxyethyl acid phosphate, 2-acryloyloxyp Polymerizable unsaturated monomers having a phosphate group such as pyracyl phosphate, 2-methacryloyloxypropyl acid phosphate; 2-hydroxy-4- (3-methacryloyloxy-2-hydroxypropoxy) benzophenone, 2-hydroxy-4- ( 3-acryloyloxy-2-hydroxypropoxy) benzophenone, 2,2'-dihydroxy-4- (3-methacryloyloxy-2-hydroxypropoxy) benzophenone, 2,2'-dihydroxy-4- (3-acryloyloxy-2 Polymerizable unsaturated monomer having an ultraviolet-absorbing functional group such as -hydroxypropoxy) benzophenone, 2- (2'-hydroxy-5'-methacryloyloxyethylphenyl) -2H-benzotriazole; 4- (meth) acryloyloxy- , 2,2,6,6-pentamethylpiperidine, 4- (meth) acryloyloxy-2,2,6,6-tetramethylpiperidine, 4-cyano-4- (meth) acryloylamino-2,2,6 , 6-tetramethylpiperidine, 1- (meth) acryloyl-4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 1- (meth) acryloyl-4-cyano-4- (meth) Acryloylamino-2,2,6,6-tetramethylpiperidine, 4-crotonoyloxy-2,2,6,6-tetramethylpiperidine, 4-crotonoylamino-2,2,6,6-tetramethylpiperidine UV-stable polymerizable unsaturated monomers such as 1-crotonoyl-4-crotonoyloxy-2,2,6,6-tetramethylpiperidine; Has a carbonyl group such as diacetone acrylamide, diacetone methacrylamide, acetoacetoxyethyl methacrylate, formyl styrene, vinyl alkyl ketone having 4 to 7 carbon atoms (for example, vinyl methyl ketone, vinyl ethyl ketone, vinyl butyl ketone) Examples thereof include polymerizable unsaturated monomer compounds, and these can be used alone or in combination of two or more.

  When a hydroxyl group-containing monomer is used as the polymerizable unsaturated monomer, a melamine resin or a polyisocyanate compound described later can be used as a crosslinking agent.

  In the case where the polymerizable unsaturated monomer uses an ultraviolet absorbing polymerizable unsaturated monomer and / or an ultraviolet stable polymerizable unsaturated monomer as at least a part of its components, an ultraviolet absorbing functional group or Since an ultraviolet-stable functional group is introduced, it is not necessary to add an ultraviolet absorber or a light stabilizer described later to the undercoat coating composition (I).

The copolymerization of the polymerizable unsaturated monomer can be carried out by a method known per se, for example, a solution polymerization method in an organic solvent. As the copolymerization method by the solution polymerization method, for example, the mixture of the monomer component and the radical polymerization initiator is dissolved or dispersed in an organic solvent, and usually at a temperature of about 80 ° C. to 200 ° C., usually about 1 to 10 hours. A method of polymerizing by heating while stirring can be mentioned.
Examples of the organic solvent that can be used for copolymerization include ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; esters such as ethyl acetate, butyl acetate, methyl benzoate, and methyl propionate; tetrahydrofuran, dioxane, dimethoxyethane, and the like. Ethers of ethylene; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate; aromatic hydrocarbons, aliphatic hydrocarbons, etc. be able to. These organic solvents can be used alone or in combination of two or more.

  The weight average molecular weight of the acrylic resin obtained as described above is not particularly limited, but is usually in the range of 1,000 to 200,000, particularly 2,000 to 100,000 from the viewpoint of weather resistance. Preferably there is.

  Here, in this specification, the weight average molecular weight uses tetrahydrofuran as a solvent, and the retention time (retention capacity) measured with a gel permeation chromatograph (“HLC8120GPC” manufactured by Tosoh Corporation) is the weight average of polystyrene. It is a value converted based on the molecular weight. Columns are “TSKgel G-4000H × L”, “TSKgel G-3000H × L”, “TSKgel G-2500H × L”, “TSKgel G-2000H × L” (both manufactured by Tosoh Corporation, trade names) ), Mobile phase: tetrahydrofuran, measurement temperature: 40 ° C., flow rate: 1 ml / min, detector: RI.

  The ultraviolet absorber has an action of suppressing the arrival of the deterioration of the film by absorbing incident light and converting light energy into a harmless form such as heat.

  As the ultraviolet absorber, conventionally known ones can be used. For example, a benzotriazole-based absorbent, a triazine-based absorbent, a salicylic acid derivative-based absorbent, a benzophenone-based absorbent, or the like can be used.

  Specific examples of the benzotriazole-based absorbent include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-5′-t-butylphenyl) benzotriazole, 2- ( 2'-hydroxy-3 ', 5'-di-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2 -(2'-hydroxy-3 ', 5'-di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3', 5'-di-t-amylphenyl) benzotriazole 2- (2′-hydroxy-4′-octoxyphenyl) benzotriazole, 2- {2′-hydroxy-3 ′-(3 ″, 4 ″, 5 ″, 6 ″ -tetrahydrophthalimi Methyl) -5'-methylphenyl} benzotriazole.

  Specific examples of the triazine-based absorbent include 2,4-bis (2,4-dimethylphenyl) -6- (2-hydroxy-4-isooctyloxyphenyl) -1,3,5-triazine, 2- [4 ((2-hydroxy-3-dodecyloxypropyl) -oxy) -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [ 4-((2-hydroxy-3-tridecyloxypropyl) -oxy) -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine and the like.

  Specific examples of the salicylic acid derivative-based absorbent include phenyl salicylate, p-octylphenyl salicylate, 4-tert-butylphenyl salicylate, and the like.

  Specific examples of the benzophenone-based absorbent include 4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-2′-carboxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone trihydrate, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-octadecyloxy Benzophenone, sodium 2,2'-dihydroxy-4,4'-dimethoxy-5-sulfobenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 5-chloro-2 -Hydroxybenzo Examples include phenone, resorcinol monobenzoate, 2,4-dibenzoyl resorcinol, 4,6-dibenzoyl resorcinol, hydroxydodecylbenzophenone, and the like. Examples of the ultraviolet absorber include known polymerizable ultraviolet absorbers such as 2- (2′-hydroxy-5′-methacryloyloxyethylphenyl) -2H-benzotriazole, 2,2′-dihydroxy-4 (3- Methacryloxy-2-hydroxypropoxy) benzophenone and the like can also be used.

  Examples of commercially available ultraviolet absorbers include TINUVIN 900, TINUVIN 928, TINUVIN 348-2, TINUVIN 479, TINUVIN 405 (trade name, manufactured by Ciba Specialty Chemicals), and RUVA 93 (trade name, manufactured by Otsuka Chemical Co., Ltd.).

  The amount of the ultraviolet absorber used in the undercoat coating composition (I) is 0.5 to 20 parts by mass, preferably 1 to 15 with respect to 100 parts by mass of the nonvolatile content of the coating composition from the viewpoint of weather resistance and the like. The range of parts by mass is appropriate.

  On the other hand, the light stabilizer is used as a radical chain inhibitor that traps active radical species generated during the deterioration process of the film, and includes, for example, a hindered amine light stabilizer.

  Among the light stabilizers, hindered piperidines may be mentioned as light stabilizers that exhibit an excellent light stabilizing action. Examples of hindered piperidines include bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl-4-piperidinyl) sebacate, and bis ( N-methyl-2,2,6,6-tetramethyl-4-piperidinyl) sebacate, 4-benzoyloxy-2,2 ′, 6,6′-tetramethylpiperidine, bis (1,2,2,6, Monomer type such as 6-pentamethyl-4-piperidyl) {[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl} butyl malonate; poly {[6- (1,1 , 3,3-tetramethylbutyl) imino-1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2 , 2,6,6-tetramethyl-4-piperidyl) iminol]} and the like; polyesters of 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol and succinic acid Examples thereof include, but are not limited to, polyester-bonded types. A known polymerizable light stabilizer can also be used as the light stabilizer.

  Commercially available products of the above light stabilizer include, for example, TINUVIN123, TINUVIN152, TINUVIN292 (trade name, manufactured by Ciba Specialty Chemicals), HOSTAVIN 3058 (trade name, manufactured by Clariant), and ADK STAB LA-82 (trade name, manufactured by ADEKA Corporation). ) And the like.

  The amount of the light stabilizer used in the undercoat coating composition (I) is from 0.1 to 10 parts by weight, preferably 0.5, based on 100 parts by weight of the nonvolatile content of the coating composition from the viewpoint of weather resistance and the like. A range of ˜5 parts by mass is suitable.

  The coating composition (I) can contain a crosslinking agent as required. The crosslinking agent has a functional group capable of reacting with the functional group in the acrylic resin, for example, melamine resin, urea resin, (block) polyisocyanate compound, epoxy compound, carboxyl group-containing compound, acid anhydride, alkoxysilane group Examples thereof include compounds.

  The undercoat coating composition (I) used in the present invention may further contain other resins and various additives as necessary, and may be diluted with a solvent as required. Examples of other resins include polyester resins, alkyd resins, urethane resins, epoxy resins, silicone resins, fluororesins, and fiber derivatives. Examples of additives include curing catalysts, polymerization inhibitors, and antioxidants. , Antifoaming agents, surface conditioners, plasticizers, pigments, fillers and the like.

  Examples of the solvent used for dilution include ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; esters such as ethyl acetate, butyl acetate, methyl benzoate, and methyl propionate; ethers such as tetrahydrofuran, dioxane, and dimethoxyethane; Examples include glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and 3-methoxybutyl acetate; aromatic hydrocarbons and aliphatic hydrocarbons. These can be used in appropriate combination depending on the purpose such as adjustment of viscosity and adjustment of coating property.

  The active energy ray-curable top coating composition (II) of the present invention contains a silsesquioxane compound (a) and a photopolymerization initiator (b).

Component (a) The silsesquioxane compound as component (a) is a silsesquioxane compound having an organic group directly bonded to a silicon atom, and is at least one of the organic groups directly bonded to the silicon atom. One is a silsesquioxane compound which is an organic group having a urethane bond and one (meth) acryloyloxy group.

  Here, in the present specification, the “silsesquioxane compound” does not mean only a silsesquioxane compound having a structure in which all Si—OH groups (hydroxysilyl groups) are hydrolyzed and condensed, but Si—OH A ladder structure in which groups remain, an incomplete cage structure, and a silsesquioxane compound of a random condensate can also be included.

  In the silsesquioxane compound (a), the ratio of the silsesquioxane compound having a structure in which all Si—OH groups are hydrolytically condensed is preferably 80% by mass or more, more preferably 90% by mass or more, and particularly preferably. Is preferably 100% by mass from the viewpoint of liquid stability and weather resistance.

  As the silsesquioxane compound (a), for example, a cissesquioxane compound in which the organic group having the urethane bond and one (meth) acryloyloxy group is an organic group represented by the following general formula (A) You can mention:

[In Formula (A), R ¹ represents a hydrogen atom or a methyl group. R ² represents a divalent hydrocarbon group having 1 to 10 carbon atoms. R ³ represents a divalent hydrocarbon group having 1 to 10 carbon atoms. Y is

(In the formula, R ² is the same as above. N represents an integer of 0 to 9).

(Wherein R ⁴ represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 6 carbon atoms), or

(Wherein R ⁵ represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 6 carbon atoms). ].

  Here, as a silsesquioxane compound (a), even if it has one type among the organic groups represented by the said general formula (A), it may have multiple types of organic groups. .

  In other words, as the silsesquioxane compound (a), for example, the organic group having the urethane bond and one (meth) acryloyloxy group is represented by the following general formulas (I) to (III). The silsesquioxane compound which is at least 1 type selected from the group which consists of can be mentioned.

[In General Formula (I), R ¹ represents a hydrogen atom or a methyl group. R ² represents a divalent hydrocarbon group having 1 to 10 carbon atoms. R ³ represents a divalent hydrocarbon group having 1 to 10 carbon atoms. n shows the integer of 0-9. ]

[In formula (II), R ^{1 to} R ³ are the same as above. R ⁴ represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 6 carbon atoms. ]

[In formula (III), R ^{1 to} R ³ are the same as above. R ⁵ represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 6 carbon atoms. ].

The R ² is not particularly limited as long as it is a divalent hydrocarbon group having 1 to 10 carbon atoms. Specifically, for example, methylene group, ethylene group, 1,2-propylene group, 1,3-propylene group, 1,2-butylene group, 1,4-butylene group, hexylene group and other alkylene groups; cyclohexylene group And aralkylene groups such as a phenylene group, a xylylene group, and a biphenylene group. Among them, a divalent hydrocarbon group having 1 to 6 carbon atoms, particularly an ethylene group, a 1,2-propylene group, and a 1,4-butylene group, have high heat resistance, scratch resistance, and high polarity polymerization. It is preferable from the viewpoint of better compatibility with unsaturated compounds.

The R ³ is not particularly limited as long as it is a divalent hydrocarbon group having 1 to 10 carbon atoms. Specifically, for example, methylene group, ethylene group, 1,2-propylene group, 1,3-propylene group, 1,2-butylene group, 1,4-butylene group, hexylene group and other alkylene groups; cyclohexylene group And aralkylene groups such as a phenylene group, a xylylene group, and a biphenylene group. Among them, a divalent hydrocarbon group having 1 to 6 carbon atoms, particularly an ethylene group or a 1,3-propylene group, is compatible with heat-resistant, scratch-resistant and highly polar polymerizable unsaturated compounds. Is preferable from the viewpoint of more excellent.

  The n is not particularly limited as long as it is an integer of 0 to 9. n is preferably an integer of 0 to 5, more preferably an integer of 0 to 3, particularly preferably 0 or 1.

The R ⁴ is not particularly limited as long as it is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 6 carbon atoms. Specifically, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, sec-butyl group, n-pentyl group, isopentyl group, neopentyl group, cyclopentyl An acyclic aliphatic monovalent hydrocarbon group or a cyclic aliphatic monovalent hydrocarbon group such as a linear or branched alkyl group such as a group, n-hexyl group, isohexyl group, cyclohexyl group; trifluoromethyl group, 3, And fluorine-containing alkyl groups such as 3,3-trifluoro-n-propyl group. In particular, a methyl group is preferable from the viewpoint of better compatibility with a highly polar polymerizable unsaturated compound.

The R ⁵ is not particularly limited as long as it is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 6 carbon atoms. Specifically, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, sec-butyl group, n-pentyl group, isopentyl group, neopentyl group, cyclopentyl An acyclic aliphatic monovalent hydrocarbon group or a cyclic aliphatic monovalent hydrocarbon group such as a linear or branched alkyl group such as a group, n-hexyl group, isohexyl group, cyclohexyl group; trifluoromethyl group, 3, And fluorine-containing alkyl groups such as 3,3-trifluoro-n-propyl group. In particular, a methyl group is preferable from the viewpoint of better compatibility with a highly polar polymerizable unsaturated compound.

As the organic group represented by the general formula (I), R ¹ is hydrogen from the viewpoint that heat resistance, scratch resistance, compatibility with a highly polar polymerizable unsaturated compound and active energy ray curability are more excellent. An organic group which is an atom, R ² is an ethylene group or a 1,4-butylene group, R ³ is an ethylene group or a 1,3-propylene group, and n is 0 is preferable.

As the organic group represented by the general formula (II), R ⁴ is methyl from the viewpoint of better heat resistance, scratch resistance, compatibility with a highly polar polymerizable unsaturated compound and active energy ray curability. And an organic group in which R ³ is an ethylene group or a 1,3-propylene group, R ¹ is a hydrogen atom, and R ² is an ethylene group.

Examples of the organic group represented by the general formula (III) include heat resistance, scratch resistance, compatibility with a highly polar polymerizable unsaturated compound, and active energy ray curability, so that R ⁵ is methyl. And an organic group in which R ³ is an ethylene group or a 1,3-propylene group, R ¹ is a hydrogen atom, and R ² is an ethylene group.

  The silsesquioxane compound (a) may be a compound having a single composition or a mixture of compounds having different compositions.

  The weight average molecular weight of the silsesquioxane compound (a) is not particularly limited. The weight average molecular weight is preferably 1,000 to 100,000, more preferably 1,000 to 10,000. These ranges are significant in terms of the heat resistance of the coating film obtained from the silsesquioxane compound (a), and the viscosity and paintability of the active energy ray-curable top coating composition (II).

  The silsesquioxane compound (a) can be produced by various methods. For example, the silsesquioxane compound (a) can be produced by the following production method A or B.

Manufacturing method A
Production method A is a production method using a starting material containing a hydrolyzable silane which is an organic group directly bonded to a silicon atom and has a urethane bond and an organic group having one (meth) acryloyloxy group Is mentioned.

  Specifically, for example, a hydrolyzable silane represented by the following general formula (IV) and, if necessary, a hydrolyzable silane other than the hydrolyzable silane represented by the following general formula (IV) are used as a starting material. And a method of producing a silsesquioxane compound (a) by hydrolytic condensation in the presence of a catalyst.

R ⁶ SiX ₃ (IV)
R ⁶ in the general formula (IV) is an organic group having a urethane bond and one (meth) acryloyloxy group. X is the same or different and represents chlorine or an alkoxy group having 1 to 6 carbon atoms.

  As a C1-C6 alkoxy group, a C1-C6 (preferably C1-C4) linear or branched alkoxy group can be mentioned. More specifically, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, 1-ethylpropoxy, isopentyloxy, neopentyloxy, n -Hexyloxy, 1,2,2-trimethylpropoxy, 3,3-dimethylbutoxy, 2-ethylbutoxy, isohexyloxy, 3-methylpentyloxy group and the like are included.

  Therefore, specific examples of X include chlorine, methoxy group, ethoxy group, propoxy group, butoxy group and the like.

  The hydrolyzable silane other than the general formula (IV) is particularly limited as long as it can produce a silsesquioxane compound by hydrolytic condensation together with the hydrolyzable silane represented by the general formula (IV). Is not to be done. Specifically, for example, alkyltrialkoxysilanes such as methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, and ethyltriethoxysilane; 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyl Examples include 3- (meth) acryloyloxypropyltrialkoxysilane such as oxypropyltriethoxysilane; vinyltrialkoxysilane such as vinyltrimethoxysilane and vinyltriethoxysilane.

  Here, the hydrolyzable silane represented by the general formula (IV) can be obtained, for example, by reacting a trialkoxysilane having an isocyanate group and a (meth) acrylic acid ester having a hydroxyl group.

  Specific examples of the hydrolyzable silane represented by the general formula (IV) include hydrolyzable silanes represented by the following general formula (V).

[In the general formula (V), R ¹ , R ² , R ³ , n and X are the same as above. ]
The hydrolyzable silane represented by the general formula (V) is obtained by, for example, reacting a hydrolyzable silane represented by the following general formula (VI) with a compound represented by the following general formula (VII). Can be obtained.

[In General Formula (VI), R ³ and X are the same as defined above. ]

[In General Formula (VII), R ¹ , R ² and n are the same as above. ]
Examples of the compound represented by the general formula (VI) include 3-isocyanatopropyltrimethoxysilane and 3-isocyanatepropyltriethoxysilane.

  Examples of the compound represented by the general formula (VII) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth). Examples include acrylate, diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, and dipropylene glycol mono (meth) acrylate.

  The reaction between the hydrolyzable silane represented by the general formula (VI) and the compound represented by the general formula (VII) can be performed according to a conventional method in which an isocyanate group and a hydroxyl group are reacted.

  The use ratio of the hydrolyzable silane represented by the general formula (VI) and the compound represented by the general formula (VII) in the above reaction formula is usually 0.90 to 1.10. About a mole, preferably about 0.95 to 1.05 mole.

  The reaction temperature is, for example, 0 to 200 ° C, preferably 20 to 200 ° C, more preferably 20 to 120 ° C. Although this reaction can be carried out regardless of pressure, a pressure range of 0.02 to 0.2 MPa, particularly 0.08 to 0.15 MPa is preferable. The reaction is usually completed in about 2 to 10 hours.

  In the reaction, a catalyst may be appropriately used. Examples of the catalyst include tertiary amines such as triethylamine and organometallic compounds such as dibutyltin dilaurate.

  In the reaction, a solvent may be appropriately used. Specific examples of the solvent include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl amyl ketone, ethyl isoamyl ketone, diisobutyl ketone, and methyl hexyl ketone; ethyl acetate, butyl acetate, methyl benzoate, propion Esters such as methyl acid; Ethers such as tetrahydrofuran, dioxane and dimethoxyethane; Glycol ethers such as propylene glycol monomethyl ether acetate and 3-methoxybutyl acetate; Aromatic hydrocarbons such as toluene and xylene; Aliphatic hydrocarbons And the like.

  In addition, other specific examples of the hydrolyzable silane represented by the general formula (IV) are represented by the hydrolyzable silane represented by the following general formula (VIII) and the following general formula (IX). Hydrolyzable silanes.

[In General Formula (VIII), R ¹ , R ² , R ³ , R ⁴ and X are the same as above. ]

[In General Formula (IX), R ¹ , R ² , R ³ , R ⁵ and X are the same as defined above. ]
The hydrolyzable silane represented by the general formula (VIII) is, for example, a product obtained by reacting a hydrolyzable silane represented by the following general formula (X) with a compound represented by the following general formula (XI). Then, the product can be further reacted with a compound represented by the following general formula (XII).

[In General Formula (X), R ³ and X are the same as above. ]

[In general formula (XI), R ⁴ is the same as defined above. ]

[In General Formula (XII), R ¹ and R ² are the same as above. ]
Specific examples of the hydrolyzable silane represented by the general formula (X) include 3-glycidoxypropyltrimethoxysilane and 3-glycidoxypropyltriethoxysilane.

  Specific examples of the compound represented by the general formula (XI) include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, trifluoroacetic acid, and 3,3,3-trifluoropropionic acid. Etc.

  Specific examples of the compound represented by the general formula (XII) include isocyanate methyl (meth) acrylate, 2-isocyanatoethyl (meth) acrylate, 3-isocyanatepropyl (meth) acrylate, and isocyanate octyl (meth). An acrylate etc. are mentioned.

  The hydrolyzable silane represented by the general formula (IX) is, for example, a product obtained by reacting a hydrolyzable silane represented by the following general formula (XIII) with a compound represented by the following general formula (XIV). Then, the product can be obtained by further reacting the product with a compound represented by the following general formula (XV).

[In General Formula (XIII), R ³ and X are the same as defined above. ]

[In general formula (XIV), R ⁵ is the same as defined above. ]

[In General Formula (XV), R ¹ and R ² are the same as above. ]
Specific examples of the hydrolyzable silane represented by the general formula (XIII) include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltri An ethoxysilane etc. are mentioned.

  Specific examples of the compound represented by the general formula (XIV) include the same compounds as those specifically shown in the description of the compound represented by the general formula (XI).

  Specific examples of the compound represented by the general formula (XV) include the same compounds as those specifically shown in the description of the compound represented by the general formula (XII).

  Reaction of the hydrolyzable silane represented by the general formula (X) with the compound represented by the general formula (XI), and the hydrolyzable silane represented by the general formula (XIII) and the general formula The reaction with the compound represented by (XIV) can be carried out according to a conventional method in which a carboxyl group and an epoxy group are reacted.

  The ratio of the hydrolyzable silane represented by the general formula (X) and the compound represented by the general formula (XI) in the above reaction is usually 0.80 to 1.20 with respect to 1 mole of the former. About a mole, preferably about 0.90 to 1.10 mole.

  In the above reaction, the proportion of the hydrolyzable silane represented by the general formula (XIII) and the compound represented by the general formula (XIV) is usually 0.80 to 1.20 with respect to 1 mole of the former. About a mole, preferably about 0.90 to 1.10 mole.

  The reaction temperature is, for example, 0 to 200 ° C, preferably 20 to 200 ° C, more preferably 20 to 120 ° C. The reaction is usually completed in about 10 to 24 hours.

  In the reaction, a catalyst may be appropriately used. Specific examples of the catalyst include tertiary amines such as triethylamine and benzyldimethylamine; quaternary ammonium salts such as tetramethylammonium chloride, tetraethylammonium bromide and tetrabutylammonium bromide; acetates and formates such as diethylamine Secondary amine salts of sodium hydroxide, alkali metal hydroxides such as sodium hydroxide and calcium hydroxide, alkali metal and alkaline earth metal salts such as sodium acetate and calcium acetate, imidazoles, diaza Examples thereof include cyclic nitrogen-containing compounds such as bicycloundecene and phosphorus compounds such as triphenylphosphine and tributylphosphine. Although the usage-amount of a catalyst is not specifically limited, It is 0.01-5 mass% with respect to the reaction raw material.

  In the reaction, a solvent may be appropriately used. The solvent is not particularly limited. Specifically, for example, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl amyl ketone, ethyl isoamyl ketone, diisobutyl ketone, methyl hexyl ketone; ethyl acetate, butyl acetate, methyl benzoate, methyl propionate, etc. Esters; ethers such as tetrahydrofuran, dioxane, dimethoxyethane; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate; toluene, xylene, etc. Aromatic hydrocarbons, aliphatic hydrocarbons and the like.

  A reaction product obtained by reacting the hydrolyzable silane represented by the general formula (X) with the compound represented by the general formula (XI) (hereinafter simply referred to as reaction product (X-XI)). And a compound represented by the general formula (XII), a hydrolyzable silane represented by the general formula (XIII) and a compound represented by the general formula (XIV). The reaction between the reaction product obtained by the reaction (hereinafter sometimes simply referred to as the reaction product (XIII-XIV)) and the compound represented by the general formula (XV) involves reacting a hydroxyl group with an isocyanate group. Can be done according to conventional methods.

  The use ratio of the reaction product (X-XI) and the compound represented by the general formula (XII) in the above reaction is usually about 0.90 to 1.10 mol of the latter with respect to 1 mol of the former, preferably What is necessary is just to be about 0.95-1.05 mol.

  The ratio of the reaction product (XIII-XIV) and the compound represented by the general formula (XV) used in the above reaction is usually about 0.90 to 1.10 moles of the latter with respect to 1 mole of the former, preferably What is necessary is just to be about 0.95-1.05 mol.

  The reaction temperature is, for example, 0 to 200 ° C, preferably 20 to 200 ° C, more preferably 20 to 120 ° C. Although this reaction can be carried out regardless of pressure, a pressure range of 0.02 to 0.2 MPa, particularly 0.08 to 0.15 MPa is preferable. The reaction is usually completed in about 2 to 10 hours.

  In the reaction, a catalyst may be appropriately used. Examples of the catalyst include tertiary amines such as triethylamine and organometallic compounds such as dibutyltin dilaurate.

  In the reaction, a solvent may be appropriately used. Specific examples of the solvent include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl amyl ketone, ethyl isoamyl ketone, diisobutyl ketone, and methyl hexyl ketone; ethyl acetate, butyl acetate, methyl benzoate, propion Esters such as methyl acid; Ethers such as tetrahydrofuran, dioxane and dimethoxyethane; Glycol ethers such as propylene glycol monomethyl ether acetate and 3-methoxybutyl acetate; Aromatic hydrocarbons such as toluene and xylene; Aliphatic hydrocarbons And the like.

In order to obtain the silsesquioxane compound of the present invention in the production method, specifically,
[1] Hydrolytic condensation using the hydrolyzable silane represented by the general formula (IV) as a starting material in the presence of a catalyst, or
[2] The hydrolyzable silane represented by the general formula (IV) and the hydrolyzable silane other than the general formula (IV) are used as starting materials and hydrolytically condensed in the presence of a catalyst.
Can be mentioned.

  As the catalyst, a basic catalyst is preferably used. Specific examples of the basic catalyst include alkali metal hydroxides such as potassium hydroxide, sodium hydroxide and cesium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethyl Examples thereof include ammonium hydroxide salts such as ammonium hydroxide and ammonium fluoride salts such as tetrabutylammonium fluoride.

  The amount of the catalyst used is not particularly limited. However, if the amount is too large, there are problems such as high cost and difficulty in removal. On the other hand, if the amount is too small, the reaction becomes slow. Therefore, the usage-amount of a catalyst becomes like this. Preferably it is 0.0001-1.0 mol with respect to 1 mol of hydrolysable silane, More preferably, it is the range of 0.0005-0.1 mol.

  In the case of hydrolytic condensation (in the case of [1] or [2] above), water is used. The quantity ratio of hydrolyzable silane and water is not particularly limited. The amount of water used is preferably 0.1 to 100 mol of water, more preferably 0.5 to 3 mol, per mol of hydrolyzable silane. If the amount of water is too small, the reaction slows down, and the yield of the desired silsesquioxane compound of the present invention may be lowered. If the amount of water is too large, the molecular weight increases and the desired structure is obtained. Product may be reduced. Moreover, when using a basic catalyst as aqueous solution, the water to be used may be substituted with the water, and water may be added separately.

  In the hydrolysis condensation, an organic solvent may be used or may not be used. It is preferable to use an organic solvent from the viewpoint of preventing gelation and adjusting the viscosity during production. As the organic solvent, polar organic solvents and nonpolar organic solvents can be used alone or as a mixture.

  As the polar organic solvent, lower alcohols such as methanol, ethanol and 2-propanol, ketones such as acetone and methyl isobutyl ketone, and ethers such as tetrahydrofuran are used. Particularly, acetone and tetrahydrofuran have a low boiling point and the system is uniform. It is preferable because the reactivity is improved. As the nonpolar organic solvent, a hydrocarbon solvent is preferable, and an organic solvent having a boiling point higher than that of water such as toluene and xylene is preferable. In particular, an organic solvent azeotropic with water such as toluene efficiently removes water from the system. This is preferable because it is possible. In particular, mixing a polar organic solvent and a nonpolar organic solvent provides the above-described advantages, so that it is preferably used as a mixed solvent.

  The reaction temperature during hydrolysis condensation is 0 to 200 ° C, preferably 10 to 200 ° C, and more preferably 10 to 120 ° C. Although this reaction can be carried out regardless of pressure, a pressure range of 0.02 to 0.2 MPa, particularly 0.08 to 0.15 MPa is preferable. The reaction is usually completed in about 1 to 12 hours.

  In the hydrolysis-condensation reaction, the condensation reaction proceeds with hydrolysis, and most of the hydrolyzable group of the hydrolyzable silane [specifically, for example, X in the general formula (IV), preferably 100%, It is liquid stability and weather resistance that it is hydrolyzed to a hydroxyl group (OH group), and further, most of the OH group, preferably 80% or more, more preferably 90% or more, particularly preferably 100%, is condensed. To preferred.

  From the mixed solution after hydrolysis condensation, the solvent, the alcohol generated by the reaction, and the catalyst may be removed by a known method. The obtained product may be further purified by removing the catalyst by various purification methods such as washing, column separation, and solid adsorbent according to the purpose. Preferably, the catalyst is removed by washing with water from the viewpoint of efficiency.

  The silsesquioxane compound (a) is produced by the above production method.

  Here, when 100% condensation is not performed in the hydrolysis condensation, the product obtained by the above production method includes a silsesquioxane having a structure in which all Si—OH groups (hydroxysilyl groups) are hydrolyzed and condensed. In addition to the compound, a silsesquioxane compound having a ladder structure in which a Si—OH group remains, an incomplete cage structure, and / or a random condensate may be included. (A) may contain those ladder structures, incomplete cage structures and / or random condensates.

Manufacturing method B
As the production method B, using a hydrolyzable silane having an epoxy group, a step B1 for producing a silsesquioxane compound having an epoxy group, an epoxy group of the silsesquioxane compound obtained by the step B1 To the second hydroxyl group of the silsesquioxane compound obtained by the second step B2 in which the carboxyl group of the compound having a carboxyl group is reacted to produce a silsesquioxane compound having a secondary hydroxyl group. And a production method including Step B3 in which the isocyanate group of the compound having a (meth) acryloyloxy group and an isocyanate group is reacted.

Step B1 Specific examples of the hydrolyzable silane having an epoxy group used in Step B1 include a hydrolyzable silane represented by the following general formula (XVI) and a general formula (XVII) below. Hydrolyzable silanes.

[In General Formula (XVI) and General Formula (XVII), R ³ and X are the same as defined above. ]
In order to obtain a silsesquioxane compound having an epoxy group in the step B1, specifically,
[3] The hydrolyzable silane represented by the general formula (XVI) and / or the hydrolyzable silane represented by the general formula (XVII) is used as a starting material for hydrolysis condensation in the presence of a catalyst. Or
[4] A hydrolyzable silane other than the hydrolyzable silane represented by the general formula (XVI) and / or the hydrolyzable silane represented by the general formula (XVII) and the hydrolyzable silane having an epoxy group. Hydrolytic condensation in the presence of a catalyst using as starting material,
Can be mentioned.

  The hydrolyzable silane other than the hydrolyzable silane having an epoxy group is particularly limited as long as it can produce a silsesquioxane compound by hydrolytic condensation together with the hydrolyzable silane having the epoxy group. It is not a thing. Specifically, for example, alkyltrialkoxysilanes such as methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, and ethyltriethoxysilane; 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyl Examples include 3- (meth) acryloyloxypropyltrialkoxysilane such as oxypropyltriethoxysilane; vinyltrialkoxysilane such as vinyltrimethoxysilane and vinyltriethoxysilane.

  As the catalyst, a basic catalyst is preferably used. Specific examples of the basic catalyst include alkali metal hydroxides such as potassium hydroxide, sodium hydroxide and cesium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethyl Examples thereof include ammonium hydroxide salts such as ammonium hydroxide and ammonium fluoride salts such as tetrabutylammonium fluoride.

  The amount of the catalyst used is not particularly limited. However, if the amount is too large, there are problems such as high cost and difficulty in removal. On the other hand, if the amount is too small, the reaction becomes slow. Therefore, the usage-amount of a catalyst becomes like this. Preferably it is 0.0001-1.0 mol with respect to 1 mol of hydrolysable silane, More preferably, it is the range of 0.0005-0.1 mol.

  In the case of hydrolytic condensation (in the case of [3] or [4] above), water is used. The quantity ratio of hydrolyzable silane and water is not particularly limited. The amount of water used is preferably 0.1 to 100 mol of water, more preferably 0.5 to 3 mol, per mol of hydrolyzable silane. If the amount of water is too small, the reaction may be slowed and the yield of the desired silsesquioxane may be reduced. If the amount of water is too large, the molecular weight will increase and the product of the desired structure will decrease. There is a risk. Moreover, when using a basic catalyst as aqueous solution, the water to be used may be substituted with the water, and water may be added separately.

  In the hydrolysis condensation, an organic solvent may be used or may not be used. It is preferable to use an organic solvent from the viewpoint of preventing gelation and adjusting the viscosity during production. As the organic solvent, polar organic solvents and nonpolar organic solvents can be used alone or as a mixture.

  As the polar organic solvent, lower alcohols such as methanol, ethanol and 2-propanol, ketones such as acetone and methyl isobutyl ketone, and ethers such as tetrahydrofuran are used. Particularly, acetone and tetrahydrofuran have a low boiling point and the system is uniform. It is preferable because the reactivity is improved. As the nonpolar organic solvent, a hydrocarbon solvent is preferable, and an organic solvent having a boiling point higher than that of water such as toluene and xylene is preferable. In particular, an organic solvent azeotropic with water such as toluene efficiently removes water from the system. This is preferable because it is possible. In particular, mixing a polar organic solvent and a nonpolar organic solvent provides the above-described advantages, so that it is preferably used as a mixed solvent.

  The reaction temperature during hydrolysis condensation is 0 to 200 ° C, preferably 10 to 200 ° C, and more preferably 10 to 120 ° C. The reaction is usually completed in about 1 to 12 hours.

  In the hydrolysis-condensation reaction, the condensation reaction proceeds with hydrolysis, and the hydrolyzable group of the hydrolyzable silane [specifically, for example, X in the general formula (XVI) or the general formula (XVII)] X Most of the OH group, preferably 100% is hydrolyzed to hydroxyl groups (OH groups), and most of the OH groups are condensed, preferably 80% or more, more preferably 90% or more, particularly preferably 100%. Is preferable from the viewpoint of liquid stability.

Step B2 In the step B2, specifically, for example, a silsesquioxane having an organic group represented by the following general formula (XVIII) as an organic group directly bonded to the silicon atom obtained in the step B1 A compound represented by the following general formula (XIX) is reacted with the compound to produce a silsesquioxane compound having an organic group represented by the following general formula (XX) as an organic group directly bonded to a silicon atom. .

[In General Formula (XVIII), General Formula (XIX), and General Formula (XX), R ³ and R ⁴ are the same as above. ]
Other specific examples include, for example, a silsesquioxane compound having an organic group represented by the following general formula (XXI) as an organic group directly bonded to the silicon atom obtained in the step B1. A compound represented by (XXII) is reacted to produce a silsesquioxane compound having an organic group represented by the following general formula (XXIII) as an organic group directly bonded to a silicon atom.

[In General Formula (XXI), General Formula (XXII), and General Formula (XXIII), R ³ and R ⁵ are the same as above. ]
A silsesquioxane compound having an organic group represented by the general formula (XX) as an organic group directly bonded to the silicon atom, and a general formula (XXIII) as an organic group directly bonded to the silicon atom. The reaction for producing the silsesquioxane compound having the organic group represented can be performed according to a conventional method in which an epoxy group and a carboxyl group are reacted.

  The reaction temperature is, for example, 0 to 200 ° C, preferably 20 to 200 ° C, more preferably 20 to 120 ° C. The reaction is usually completed in about 10 to 24 hours.

  The ratio of the silsesquioxane compound having an organic group represented by the general formula (XVIII) and the compound represented by the general formula (XIX) in the above reaction is represented by the general formula ( The compound represented by the general formula (XIX) is usually about 0.80 to 1.20 moles, preferably about 0.90 to 1.10 moles per mole of the organic group represented by XVIII). Good.

  The ratio of the silsesquioxane compound having an organic group represented by the general formula (XXI) and the compound represented by the general formula (XXII) in the above reaction is represented by the general formula ( The compound represented by the general formula (XXII) is usually about 0.80 to 1.20 moles, preferably about 0.80 to 1.20 moles per mole of the organic group represented by XXI). Good.

  In the reaction, a catalyst may be appropriately used. Specific examples of the catalyst include tertiary amines such as triethylamine and benzyldimethylamine; quaternary ammonium salts such as tetramethylammonium chloride, tetraethylammonium bromide and tetrabutylammonium bromide; acetates and formates such as diethylamine Secondary amine salts of sodium hydroxide, alkali metal hydroxides such as sodium hydroxide and calcium hydroxide, alkali metal and alkaline earth metal salts such as sodium acetate and calcium acetate, imidazoles, diaza Examples thereof include cyclic nitrogen-containing compounds such as bicycloundecene and phosphorus compounds such as triphenylphosphine and tributylphosphine. Although the usage-amount of a catalyst is not specifically limited, It is 0.01-5 mass% with respect to the reaction raw material.

  In the reaction, a solvent may be appropriately used. The solvent is not particularly limited. Specifically, for example, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl amyl ketone, ethyl isoamyl ketone, diisobutyl ketone, methyl hexyl ketone; ethyl acetate, butyl acetate, methyl benzoate, methyl propionate, etc. Esters; ethers such as tetrahydrofuran, dioxane, dimethoxyethane; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate; toluene, xylene, etc. Aromatic hydrocarbons, aliphatic hydrocarbons and the like.

Step B3 In the step B3, specifically, for example, a silsesquioxane having an organic group represented by the general formula (XX) as an organic group directly bonded to the silicon atom obtained in the step B2 The compound is reacted with a compound represented by the following general formula (XXIV).

[In General Formula (XXIV), R ¹ and R ² are the same as defined above. ]
By carrying out this reaction, a silsesquioxane compound having an organic group represented by the general formula (II) as an organic group directly bonded to a silicon atom can be obtained.

  As another specific example, for example, a silsesquioxane compound having an organic group represented by the above general formula (XXIII) as an organic group directly bonded to a silicon atom obtained in the step B2 can be represented by the following general formula. The compound represented by (XXV) is reacted.

[In General Formula (XXV), R ¹ and R ² are the same as above. ]
By performing this reaction, a silsesquioxane compound having an organic group represented by the general formula (III) as an organic group directly bonded to a silicon atom can be obtained.

  The reaction temperature of the reaction can be carried out according to a conventional method for reacting a hydroxyl group with an isocyanate group, and is, for example, 0 to 200 ° C, preferably 10 to 200 ° C, and more preferably 10 to 120 ° C. The reaction is usually completed in about 2 to 10 hours.

  The use ratio of the silsesquioxane compound having an organic group represented by the general formula (XX) and the compound represented by the general formula (XXIV) in the above reaction is represented by the general formula ( XX) The amount of the compound represented by the general formula (XXIV) is usually about 0.90 to 1.10 mol, preferably about 0.95 to 1.05 mol with respect to 1 mol of the organic group represented by XX). Good.

  The ratio of the silsesquioxane compound having an organic group represented by the general formula (XXIII) and the compound represented by the general formula (XXV) in the above reaction is represented by the general formula ( XXIII) The amount of the compound represented by the general formula (XXV) is usually about 0.90 to 1.10 mol, preferably about 0.95 to 1.05 mol with respect to 1 mol of the organic group represented by XXIII). Good.

  In the reaction, a catalyst may be appropriately used. Examples of the catalyst include tertiary amines such as triethylamine and organometallic compounds such as dibutyltin dilaurate.

  The silsesquioxane compound (a) is produced by the above production method.

  The target compound obtained by the above reactions can be separated from the reaction system by ordinary separation means and further purified. As this separation and purification means, for example, distillation method, solvent extraction method, dilution method, recrystallization method, column chromatography, ion exchange chromatography, gel chromatography, affinity chromatography, etc. can be used.

  Here, in the case where 100% condensation is not performed in the hydrolysis and condensation in the B1 step, the product obtained by the production method B includes a silyl having a structure in which all Si—OH groups (hydroxysilyl groups) are hydrolyzed and condensed. In addition to the sesquioxane compound, a silsesquioxane compound having a ladder structure in which Si—OH groups remain, an incomplete cage structure and / or a random condensate may be included. The sesquioxane compound (a) may contain a ladder structure, an incomplete cage structure and / or a random condensate.

The component (b) photopolymerization initiator (b) can be used without any particular limitation as long as it is an initiator that absorbs active energy rays and generates radicals.

  Examples of the photopolymerization initiator (b) include α-diketones such as benzyl and diacetyl; acyloins such as benzoin; acyloin ethers such as benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether; thioxanthone, 2, 4 -Thioxanthones such as diethylthioxanthone, 2-isopropylthioxanthone, thioxanthone-4-sulfonic acid; Benzophenones such as benzophenone, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone; Michler's ketone Acetophenone, 2- (4-toluenesulfonyloxy) -2-phenylacetophenone, p-dimethylaminoacetophenone, α, α'-dimethoxyacetoxybenzophenone, 2,2'-dimeth Ci-2-phenylacetophenone, p-methoxyacetophenone, 2-methyl [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) Acetophenones such as 1-butan-1-one, α-isohydroxyisobutylphenone, α, α'-dichloro-4-phenoxyacetophenone, 1-hydroxy-cyclohexyl-phenyl-ketone; 2,4,6-trimethylbenzoyldiphenylphosphine Acylphosphine oxides such as oxide and bis (acyl) phosphine oxide; Quinones such as anthraquinone and 1,4-naphthoquinone; Halo such as phenacyl chloride, trihalomethylphenylsulfone, tris (trihalomethyl) -s-triazine Emissions compounds; peroxides such as di -t- butyl peroxide and the like. These can be used as one or a mixture of two or more.

  Examples of commercially available photopolymerization initiators (b) include IRGACURE-184, IRGACURE-127, IRGACURE-261, IRGACURE-500, IRGACURE-651, IRGACURE-819, IRGACURE-907, IRGACURE-CGI-. 1700 (trade name, manufactured by Ciba Specialty Chemicals), Darocur-1173, Darocur-1116, Darocur-2959, Darocur-1664, Darocur-4043 (trade name, manufactured by Merck Japan), KAYACURE-MBP , Kayacure-DETX-S, Kayacure-DMBI, Kayacure-EPA, Kayacure-OA (Nippon Kayaku Co., Ltd., trade name), Vicure-10, Vicure-55 (STAUFFER Co., LTD.) Product, trade name), Trigona (TRIGONAL) P1 [manufactured by AKZO Co., LTD., Product name], SANDORAY 1000 [manufactured by SANDOZ Co., LTD., Product name], Deep (DEAP) [APGEON (APJOHN Co., LTD., Trade name), CANTACURE-PDO, KANTACURE-ITX, KANTACURE-EPD (trade name, manufactured by WARD BLEKINSOP Co., LTD.), ESACURE -KIP150, ESACURE-ONE (trade name, manufactured by LAMBERTI), Lucillin-TPO and the like.

  The photopolymerization initiator (b) is preferably one or a mixture of two or more of thioxanthones, acetophenones and acylphosphine oxides from the viewpoint of photocurability. Particularly preferred are mixtures with fin oxides.

  The proportion of the silsesquioxane compound (a) and the photopolymerization initiator (b) used is not particularly limited. Usually, the latter may be 1 to 20 parts by mass, preferably 2 to 10 parts by mass with respect to 100 parts by mass of the former non-volatile content.

  The active energy ray-curable top coating composition (II) used in the present invention essentially comprises the components (a) and (b), and, if necessary, polymerizable properties other than the component (a). An unsaturated compound (c) can be contained.

  The polymerizable unsaturated compound (c) is not particularly limited as long as it is a compound other than the silsesquioxane compound of the present invention and has at least one polymerizable unsaturated double bond in its chemical structure. .

  Examples of the polymerizable unsaturated compound (c) include esterified products of monohydric alcohol and (meth) acrylic acid. Specifically, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (Meth) acrylate, neopentyl (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, N-acryloyloxyethylhexahydro Examples include phthalimide. Moreover, for example, an esterified product of a polyhydric alcohol and (meth) acrylic acid can be used. Specifically, for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1,3-butanediol di (meth) Acrylate, 1,4-butanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, glycerin di (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol di (meth) acrylate, Dipentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, pentaerythritol di (meth) acrylate, bisphenol A ethylene oxide modified di (meth) acrylate, etc. Meth) acrylate compounds; glycerin tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane propylene oxide modified tri (meth) acrylate, trimethylolpropane ethylene oxide modified tri (meth) acrylate, pentaerythritol tri (meth) ) Acrylate, tris (2-acryloyloxyethyl) isocyanurate, tris (2-acryloyloxypropyl) isocyanurate, ε-caprolactone modified tris (acryloxyethyl) isocyanurate, 1,6-hexamethylene diisocyanate isocyanurate ring addition Product and hydroxyalkyl (meth) acrylate equimolar reaction product, having iminooxadiazinedione group-hexamethylene diisocyanate Triisocyanate compound such as equimolar reaction product of isocyanurate cycloadduct of hydroxyate and hydroxyalkyl (meth) acrylate; tetra (meth) acrylate compound such as pentaerythritol tetra (meth) acrylate; Examples include pentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate. Furthermore, urethane (meth) acrylate resin, epoxy (meth) acrylate resin, polyester (meth) acrylate resin and the like can be mentioned. The urethane (meth) acrylate resin is prepared by, for example, using a polyisocyanate compound, a hydroxylalkyl (meth) acrylate, and a polyol compound as raw materials, and reacting them in an amount such that the hydroxyl group is equimolar or excessive with respect to the isocyanate group. Obtainable. These polymerizable unsaturated compounds can be used alone or in combination of two or more.

  Although the usage-amount in the case of containing the said polymerizable unsaturated compound (c) is not specifically limited, From the point of the physical property of the coating film obtained, the non volatile matter of 100 mass of the said silsesquioxane compound (a) 0.1-1000 mass parts is preferable with respect to parts, and 1-200 mass parts is more preferable.

  In addition, the active energy ray-curable top coating composition (II) used in the present invention may contain colloidal silica as necessary from the viewpoint of improving scratch resistance and abrasion resistance. Colloidal silica is usually obtained by dispersing ultrafine particles of silicic anhydride having a primary particle diameter of 1 to 200 mμ in water or an organic solvent. Such colloidal silica may be treated with a hydrolyzable silane compound or a polymerizable silane compound.

  Although the usage-amount in the case of containing the said colloidal silica is not specifically limited, The said silsesquioxane compound (a) from the point of the abrasion resistance of a coating film obtained, an abrasion-resistant improvement, and a crack prevention. 1-60 mass parts is preferable with respect to 100 mass parts of non-volatile content of 5-30 mass parts.

  The active energy ray-curable top coating composition (II) used in the present invention may further contain various additives, saturated resins, etc., if necessary, and may be diluted with a solvent as required. Examples of the additive include a sensitizer, an ultraviolet absorber, a light stabilizer, a polymerization inhibitor, an antioxidant, an antifoaming agent, a surface conditioner, a plasticizer, and a colorant. Examples of the saturated resin include saturated acrylic resin, saturated polyester resin, saturated urethane resin, and the like. As an ultraviolet absorber and a light stabilizer, it can use suitably selecting from what was listed by description of the above-mentioned undercoat coating composition (I).

  Examples of the solvent used for dilution include ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; esters such as ethyl acetate, butyl acetate, methyl benzoate, and methyl propionate; ethers such as tetrahydrofuran, dioxane, and dimethoxyethane; Examples include glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and 3-methoxybutyl acetate; aromatic hydrocarbons and aliphatic hydrocarbons. These can be used in appropriate combination depending on the purpose such as adjustment of viscosity and adjustment of coating property.

The nonvolatile content of the active energy ray-curable top coating composition (II) is not particularly limited. For example, Preferably it is 20-100 mass%, More preferably, it is 25-70 mass%. These ranges are significant in terms of smoothness of the coating film and shortening of the drying time.

  In the method for forming a multilayer coating film of the present invention, an undercoating film is formed on a substrate using the above-mentioned room temperature curing or thermosetting undercoating composition (I), and then the above-mentioned active energy is formed thereon. An overcoating film is formed using the wire curable top coating composition (II).

  The substrate to which the method of the present invention is applied is not particularly limited. For example, metal materials such as iron, aluminum, brass, copper, stainless steel, tinplate, galvanized steel, alloyed zinc (Zn-Al, Zn-Ni, Zn-Fe, etc.) plated steel; polyethylene resin, polypropylene resin, acrylonitrile -Butadiene-styrene (ABS) resin, polyamide resin, acrylic resin, vinylidene chloride resin, polycarbonate resin, polyurethane resin, epoxy resin and other plastic materials such as FRP; glass, cement, concrete and other inorganic materials; wood A fiber material (paper, cloth, etc.) and the like. Among them, a plastic material is preferable, and a polycarbonate resin is particularly preferable.

  Further, the use of the coated article obtained by the method of the present invention is not particularly limited. For example, the outer plate of an automobile body such as a passenger car, a truck, a motorcycle, and a bus; automobile parts; Examples of the outer plate portion of the product and the like. Among them, the outer plate portion of the automobile body and the automobile part are preferable.

  The method for applying the room temperature curing or thermosetting primer coating composition (I) to the above-mentioned substrate is not particularly limited. For example, roller coating, roll coater coating, spin coater coating, curtain roll coater coating, slitting. Examples include coater coating, spray coating, electrostatic coating, dip coating, silk printing, and spin coating. The film thickness of the coating film is appropriately set according to the purpose. For example, the film thickness is preferably 3 to 50 μm, more preferably 5 to 40 μm. When the film thickness is at least the lower limit of these ranges, the coating film is excellent in smoothness and appearance. Moreover, when it is below the upper limit value of these ranges, the curability and crack resistance of the coating film are excellent.

  When forming a coating film from the room temperature curing or thermosetting undercoating composition (I), preheating, air blowing, etc. in order to reduce or remove the volatile content of the coating film immediately after coating It can be performed. The preheating can be usually performed by directly or indirectly heating the coated object to be coated in a drying furnace at a temperature of 50 to 110 ° C., preferably 60 to 90 ° C. for 1 to 30 minutes. Moreover, air blow can be normally performed by spraying the air heated to normal temperature or the temperature of 25 to 80 degreeC on the coating surface of the to-be-coated object.

  As described above, after drying as necessary, a cured coating film may be formed by heating, or the top coating composition of the next step may be applied in a dry / uncured state.

  There are no particular limitations on the heating conditions for curing the coating film of the room temperature curing or thermosetting primer coating composition (I). For example, it can be heated at a temperature of 50 to 140 ° C. for 1 to 60 minutes.

  The method of applying the active energy ray-curable top coating composition (II) on the undercoat film formed as described above is not particularly limited. For example, roller coating, roll coater coating, spin coater coating , Curtain roll coater coating, slit coater coating, spray coating, electrostatic coating, immersion coating, silk printing, spin coating and the like.

  When forming a coating film from the said active energy ray hardening-type top coat composition (II), it can dry as needed. The drying is not particularly limited as long as the solvent that is added can be removed. For example, it can be performed at a drying temperature of 20 to 100 ° C. for a drying time of 3 to 20 minutes.

  The film thickness of the coating film is appropriately set according to the purpose. For example, the film thickness is preferably 1 to 15 μm, and more preferably 2 to 10 μm. When the film thickness is at least the lower limit of these ranges, the coating film is excellent in smoothness and appearance. Moreover, when it is below the upper limit value of these ranges, the curability and crack resistance of the coating film are excellent.

After drying as needed as described above, active energy ray irradiation is performed to form a cured coating film. The irradiation source and irradiation amount of active energy ray irradiation are not particularly limited. For example, the active energy ray irradiation source includes ultra-high pressure, high pressure, medium pressure, low pressure mercury lamp, chemical lamp, carbon arc lamp, xenon lamp, metal halide lamp, fluorescent lamp, tungsten lamp, sunlight and the like. Dose, for example preferably 100~10000mJ / cm ^2, more preferably include a range of 500~5000mJ / cm ^2.

  The active energy ray irradiation may be performed in an air atmosphere or in an inert gas atmosphere. Examples of the inert gas include nitrogen and carbon dioxide. Active energy ray irradiation in an inert gas atmosphere is preferable from the viewpoint of curability.

  Moreover, you may heat a coating film as needed after active energy ray irradiation. By heating, distortion of the coating film generated by curing of the coating film by active energy ray irradiation can be alleviated. Further, the heating may improve the hardness or adhesion of the coating film. Heating can usually be performed at an ambient temperature of 150 to 250 ° C. for 1 to 30 minutes.

  Hereinafter, the present invention will be described in more detail with reference to examples. “Part” and “%” indicate “part by mass” and “% by mass” unless otherwise specified. In addition, the structural analysis and measurement in the production example were performed by the following analyzer and measurement method in addition to the analyzer described in this specification.

( ²⁹ Si-NMR, ¹ H-NMR analysis)
Apparatus: FT-NMR EX-400 manufactured by JEOL
Solvent: CDCl ₃
Internal standard: Tetramethylsilane (FT-IR analysis)
Apparatus: FT / IR-610 manufactured by JASCO Corporation.

(SP value measurement method)
The SP value in this example is a solubility parameter, which can be measured by cloud point titration, which is a simple measurement method. W. SUH, J. et al. M.M. It is a value calculated according to the CORBETT equation (see description of Journalof Applied Polymer Science, 12, 2359, 1968).
Formula SP = (√Vml · δH + √Vmh · δD) / (√Vml + √Vmh)
In cloud point titration, when 0.5 g of sample was dissolved in 10 ml of acetone, n-hexane was added and the titration amount H (ml) at the cloud point was read, and similarly deionized water was added to the acetone solution. The titration amount D (ml) at the cloud point is read and applied to the following formula to calculate Vml, Vmh, δH, and δD. The molecular volume (mol / ml) of each solvent is acetone: 74.4, n-hexane: 130.3, deionized water: 18, and SP of each solvent is acetone: 9.75, n- Hexane: 7.24, deionized water: 23.43.
Vml = 74.4 × 130.3 / ((1−VH) × 130.3 + VH × 74.4)
Vmh = 74.4 × 18 / ((1−VD) × 18 + VD × 74.4)
VH = H / (10 + H)
VD = D / (10 + D)
δH = 9.75 × 10 / (10 + H) + 7.24 × H / (10 + H)
δD = 9.75 × 10 / (10 + D) + 23.43 × D / (10 + D).

Production of Silsesquioxane Compound (a) (Production Example 1)
A separable flask equipped with a reflux condenser, a thermometer, an air introduction tube, and a stirrer was charged with 685 parts of 3-isocyanatopropyltriethoxysilane, 315 parts of 2-hydroxyethyl acrylate, and 1 part of p-methoxyphenol, and dried air was added. The mixture was reacted at 100 ° C. for 12 hours while blowing to obtain a product (P1). Next, 728 parts of the product (P1) and 2800 parts of tetrahydrofuran were placed in a separable flask equipped with a reflux condenser, a thermometer, and a stirrer, and stirred at room temperature. 4 parts of tetrarabutylammonium fluoride trihydrate was dissolved in 54 parts of deionized water and charged into a flask, and reacted at 20 ° C. for 24 hours. After adding 500 parts of 1-methoxy-2-propanol and removing volatiles by distillation under reduced pressure, 500 parts of 1-methoxy-2-propanol was further added and distilled under reduced pressure, and the solvent was exchanged. The product was adjusted to 1000 parts to obtain 1000 parts of a 50% non-volatile solution of the product (P2).

As a result of ²⁹ Si-NMR analysis of the product (P2), only a peak around −70 ppm derived from the T3 structure in which all three oxygen atoms bonded to Si were bonded to other Si was confirmed, and T0, T1 No peak derived from the T2 structure was observed.

As a result of ¹ H-NMR analysis of the product (P2), a peak of 0.6 ppm derived from a methylene group bonded to Si was confirmed. In addition, 5.9 ppm, 6.1 ppm, and 6.4 ppm peaks derived from the carbon-carbon unsaturated bond of the acryloyloxy group were confirmed. The molar ratio of the carbon-carbon unsaturated bond of the acryloyloxy group to the methylene group bonded to Si calculated from these peak intensity ratios was 1.01.

Moreover, as a result of conducting FT-IR analysis about the product (P2), the peak of 1540cm < ^-1 > vicinity which belongs to a urethane bond was confirmed.

  Moreover, as a result of performing a gel permeation chromatograph (GPC) analysis about the product (P2), the weight average molecular weight was 2,500.

From the ²⁹ Si-NMR, ¹ H-NMR, FT-IR, and GPC results for the product (P2), all of the organic groups in which the product (P2) was directly bonded to the silicon atom were represented by the following formula (XXVI ) Organic group

It is confirmed that the silsesquioxane compound is a silsesquioxane compound having a weight average molecular weight of 2,500, wherein the silsesquioxane compound has a structure in which almost all Si—OH groups are hydrolyzed and condensed. It was done. The resulting silsesquioxane compound had an SP value of 10.7.

(Production Example 2)
In a separable flask equipped with a reflux condenser, a thermometer, an air introduction tube, and a stirrer, 646 parts of 3-isocyanatopropyltriethoxysilane, 363 parts of 4-hydroxybutyl acrylate, and 1 part of p-methoxyphenol were charged, and dry air was supplied. The mixture was reacted at 100 ° C. for 12 hours while blowing to obtain a product (P3). Next, 706 parts of the product (P3) and 2800 parts of tetrahydrofuran were placed in a separable flask equipped with a reflux condenser, a thermometer, and a stirrer, and stirred at room temperature. 4 parts of tetrarabutylammonium fluoride trihydrate was dissolved in 48 parts of deionized water and charged into the flask, and reacted at 20 ° C. for 24 hours. After adding 500 parts of 1-methoxy-2-propanol and removing volatiles by distillation under reduced pressure, 500 parts of 1-methoxy-2-propanol was further added and distilled under reduced pressure, and the solvent was exchanged. The product was adjusted to 1000 parts to obtain 1000 parts of a 50% nonvolatile solution of the product (P4).

As a result of ²⁹ Si-NMR analysis of the product (P4), only a peak around −70 ppm derived from the T3 structure in which all three oxygen atoms bonded to Si were bonded to other Si was confirmed, and T0, T1 No peak derived from the T2 structure was observed.

Further, as a result of ¹ H-NMR analysis of the product (P4), a peak of 0.6 ppm derived from a methylene group bonded to Si was confirmed. In addition, 5.9 ppm, 6.1 ppm, and 6.4 ppm peaks derived from the carbon-carbon unsaturated bond of the acryloyloxy group were confirmed. The molar ratio of the carbon-carbon unsaturated bond of the acryloyloxy group to the methylene group bonded to Si calculated from these peak intensity ratios was 1.02.

Moreover, as a result of conducting FT-IR analysis about the product (P4), the peak of 1540cm < ^-1 > vicinity which belongs to a urethane bond was confirmed.

  Moreover, as a result of performing GPC analysis about a product (P4), the weight average molecular weight was 3,000.

From the ²⁹ Si-NMR, ¹ H-NMR, FT-IR, and GPC results for the product (P4), all of the organic groups in which the product (P4) was directly bonded to the silicon atom were represented by the following formula (XXVII). ) Organic group

It is confirmed that the silsesquioxane compound is a silsesquioxane compound having a weight average molecular weight of 3,000 having a structure in which almost all Si—OH groups are hydrolyzed and condensed. It was done. The SP value of the obtained silsesquioxane compound was 10.5.

(Production Example 3)
In a separable flask equipped with a reflux condenser, a thermometer, an air introduction tube, and a stirrer, 246 parts of the product (P1), 470 parts of acryloxypropyltrimethoxysilane, and 2800 parts of tetrahydrofuran were added and stirred at room temperature. 4 parts of tetrarabutylammonium fluoride trihydrate was dissolved in 70 parts of deionized water and charged into a flask, and reacted at 20 ° C. for 24 hours while blowing dry air. After adding 500 parts of 1-methoxy-2-propanol and removing volatiles by distillation under reduced pressure, 500 parts of 1-methoxy-2-propanol was further added and distilled under reduced pressure, and the solvent was exchanged. The product was adjusted to 1000 parts to obtain 1000 parts of a 50% nonvolatile solution of the product (P5).

As a result of ²⁹ Si-NMR analysis of the product (P5), only a peak around −70 ppm derived from the T3 structure in which all three oxygen atoms bonded to Si were bonded to other Si was confirmed, and T0, T1 No peak derived from the T2 structure was observed.

As a result of ¹ H-NMR analysis of the product (P5), a peak of 0.6 ppm derived from a methylene group bonded to Si was confirmed. In addition, 5.9 ppm, 6.1 ppm, and 6.4 ppm peaks derived from the carbon-carbon unsaturated bond of the acryloyloxy group were confirmed. The molar ratio of the carbon-carbon unsaturated bond of the acryloyloxy group to the methylene group bonded to Si calculated from these peak intensity ratios was 1.01.

Moreover, as a result of conducting FT-IR analysis about the product (P5), the peak of 1540cm < ^-1 > vicinity which belongs to a urethane bond was confirmed.

  Moreover, as a result of performing a gel permeation chromatograph (GPC) analysis about the product (P5), the weight average molecular weight was 2,000.

From the results of the ²⁹ Si-NMR, ¹ H-NMR, FT-IR, and GPC for the product (P5), 25 mol% of the organic group in which the product (P5) is directly bonded to the silicon atom is represented by the above formula. In the organic group represented by (XXVI), the remaining 75 mol% is represented by the following formula (XXIX)

It is confirmed that the silsesquioxane compound is a silsesquioxane compound having a weight average molecular weight of 2,000, which is a structure in which almost all Si—OH groups are hydrolytically condensed. It was done. The SP value of the obtained silsesquioxane compound was 10.4.

(Production Example 4)
A separable flask equipped with a reflux condenser, thermometer, air inlet tube, and stirrer was charged with 100 parts of Glycidyl POSS cage mixture (trade name, manufactured by Hybrid Plastics) and 140 parts of butyl acetate, and dissolved while stirring at 60 ° C. I let you. 40 parts of acetic acid, 0.5 part of p-methoxyphenol, and 10 parts of tetrabutylammonium bromide were added thereto, and reacted at 120 ° C. for 12 hours while blowing dry air. After cooling to 80 ° C. and adding 85 parts of 2-isocyanatoethyl acrylate and reacting at 80 ° C. for 10 hours, volatiles were removed by distillation under reduced pressure, and 500 g of 1-methoxy-2-propanol was added to further reduce the pressure. Distillation gave a 50% non-volatile solution of the product (P6).

  The Glycidyl POSS cage mixture used as a raw material was a 3-glycidoxypropyl group-containing cage-type polysilsesquioxane, the weight average molecular weight was 1,800, and the epoxy equivalent was 168 g / eq.

As a result of ²⁹ Si-NMR analysis of the product (P6), only a peak near −70 ppm derived from the T3 structure in which all three oxygen atoms bonded to Si were bonded to other Si was confirmed. No peak derived from the T1 or T2 structure indicating the presence of was observed.

Further, as a result of ¹ H-NMR analysis of the product (P6), a peak of 0.6 ppm derived from a methylene group bonded to Si was confirmed. In addition, 5.9 ppm, 6.1 ppm, and 6.4 ppm peaks derived from the carbon-carbon unsaturated bond of the acryloyloxy group were confirmed. The molar ratio of the carbon-carbon unsaturated bond of the acryloyloxy group to the methylene group bonded to Si calculated from these peak intensity ratios was 1.00. Moreover, the peak attributed to an epoxy group was not confirmed. The epoxy equivalent determined by titration was 10,000 g / eq or more.

Moreover, as a result of performing FT-IR analysis about the product (P6), a broad peak around 1540 cm ⁻¹ attributed to a urethane bond that was not confirmed in the raw material Glycidyl POSS cage mixture was confirmed.

  Moreover, as a result of performing GPC analysis about a product (P6), the weight average molecular weight was 4,000.

From the ²⁹ Si-NMR, ¹ H-NMR, FT-IR, and GPC results for the product (P6), all of the organic groups in which the product (P6) was directly bonded to the silicon atom were represented by the following formula (XXVIII). ) Organic group

A silsesquioxane compound having a weight average molecular weight of 4,000 in which at least 55% of the silsesquioxane compound has a structure in which all Si—OH groups are hydrolyzed and condensed. It was confirmed. The SP value of the obtained silsesquioxane compound was 11.2.

Production and production example 5 of acrylic resin for undercoat paint (I)
A glass reaction vessel equipped with a heating device, a stirrer, a thermometer, and a reflux condenser was charged with 50 parts of 1-methoxy-2-propanol, heated and stirred, and maintained at 100 ° C. In this, 36 parts of methyl methacrylate, 30 parts of isobornyl acrylate, 10 parts of n-butyl methacrylate, KBM-503 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., γ-methacryloyloxypropyltrimethoxysilane), 15 parts, 2- (2'-hydroxy-5'-methacryloyloxyethylphenyl) -2H-benzotriazole 8 parts, 4-methacryloyloxy-2,2,6,6-tetramethylpiperidine 1 part, azobisisobutyronitrile 2 parts and A mixture consisting of 50 parts of 1-methoxy-2-propanol was added dropwise over 3 hours. After completion of the dropwise addition, the mixture was aged at 100 ° C. for 30 minutes, and then an additional catalyst mixture composed of 10 parts of 1-methoxy-2-propanol and 0.2 parts of azobisisobutyronitrile was added dropwise over 1 hour. Next, after aging at 100 ° C. for 1 hour, 40 parts of 1-methoxy-2-propanol was added and cooled to obtain an acrylic resin (i-1) solution having a nonvolatile content of 40%.

Production Examples 6 to 10
In the said manufacture example 5, except having set it as the monomer mixing | blending shown in Table 1, operation similar to manufacture example 5 was performed and acrylic resin solution (i-2)-(i-6) was obtained. Table 1 shows the nonvolatile content and the weight average molecular weight of these acrylic resin solutions.

Preparation preparation example 1 of undercoat paint composition (I)
250 parts of a 40% acrylic resin solution obtained in Production Example 1 (non-volatile content: 100 parts), TINUVIN 928 (trade name, manufactured by Ciba Specialty Chemicals, Inc., UV absorber), TINUVIN 479 (trade name, manufactured by Ciba Specialty Chemicals) , UV absorber) 4 parts, TINUVIN 123 (trade name, manufactured by Ciba Specialty Chemicals, Inc., light stabilizer), and 0.05 part BYK-315 (trade name, manufactured by BYK Chemie) as a surface conditioner are uniformly mixed. Then, the nonvolatile content was adjusted with 1-methoxy-2-propanol to obtain an undercoat coating composition (I-1) having a nonvolatile content of 30%.

Creation examples 2 to 10
In Preparation Example 1, undercoat paint compositions (I-2) to (I-) were prepared in the same manner as in Preparation Example 1, except that the types and amounts of each component were changed to the types and amounts of each component shown in Table 2. 10) was obtained. In addition, the compounding quantity of Table 2 shows the compounding quantity of a non volatile matter. (Note 1) to (Note 2) are as follows.

(Note 1) Sumidur N-3300: trade name, manufactured by Sumika Bayer Urethane Co., Ltd., isocyanurate-modified hexamethylene diisocyanate, solid content 100%
(Note 2) Cymel 235: trade name, manufactured by Mitsui Cytec, methylated / butylated melamine resin

Example 11 for preparing active energy ray-curable top coating composition (II)
200 parts of product (P2) solution obtained in Production Example 1 (100 parts of non-volatile content), Irgacure-184 (trade name, manufactured by Ciba Specialty Chemicals, 1-hydroxy-cyclohexyl-phenyl-ketone), Irgacure- 819 (trade name, manufactured by Ciba Specialty Chemicals, 2,4,6-trimethylbenzoyldiphenylphosphine oxide) 1 part, RUVA 93 (trade name, manufactured by Otsuka Chemical Co., Ltd., UV absorber) 2 parts, TINUVIN 123 (trade name, Ciba Mix 1 part of Specialty Chemicals, light stabilizer) and 0.5 part of BYK-3500 (trade name, manufactured by Big Chemie) as a surface conditioner, and adjust the non-volatile content with 1-methoxy-2-propanol. An active energy ray-curable top coating composition (II-1) having a nonvolatile content of 30% was obtained. .

Creation examples 12-26
In Preparation Example 11, the active energy ray-curable top coating composition (II-2) was prepared in the same manner as in Preparation Example 11 except that the types and amounts of each component were changed to the types and amounts of each component shown in Table 3. ) To (II-16) were obtained.

  In addition, the compounding quantity of the said Table 3 is a compounding quantity of a non volatile matter. (Note 3) to (Note 11) are as follows.

(Note 3) Ebecryl 1290k: trade name, manufactured by Daicel-Cytec, urethane acrylate (Note 4) Aronix-M408: trade name, manufactured by Toagosei, ditrimethylolpropane tetraacrylate (Note 5) Aronix M-315: trade name, Toagosei Co., Ltd., a mixture of bis (2-acryloyloxyethyl) hydroxyethyl isocyanurate and tris (2-acryloyloxyethyl) isocyanurate (Note 6) IRR214K: trade name, manufactured by Daicel Cytec, Methanol dimethacrylate (Note 7) MEK-ST: trade name, manufactured by Nissan Chemical Co., Ltd., colloidal silica.

  (Note 8) Polymerizable silane-modified colloidal silica: produced as follows. In a separable flask equipped with a reflux condenser, a thermometer, an air introduction tube and a stirrer, colloidal silica fine particles (dispersion medium: isopropanol, silica concentration: 30% by mass, average primary particle size: 12 nm, trade name: IPA-ST, Nissan Chemical Industries, Ltd.) 333 parts (silica fine particles 100 parts), 3-methacryloyloxypropyltrimethoxysilane 10 parts, p-methoxyphenol 0.2 parts and isopropanol 233 parts, and then blown in dry air and stirred While raising the temperature. When the reflux of volatile components began, propylene glycol monomethyl ether was added and azeotropically distilled to replace the solvent in the reaction system. Subsequently, after performing a dehydration condensation reaction with stirring at 95 ° C. for 2 hours, the temperature was lowered to 60 ° C., 0.03 part of tetrabutylammonium fluoride was added, and the mixture was further reacted with stirring for 1 hour. After completion of the reaction, volatile components were distilled off under reduced pressure, and propylene glycol monomethyl ether was further added for azeotropic distillation. The solvent was replaced by adding propylene glycol monomethyl ether and performing azeotropic distillation several times to obtain a 40% nonvolatile dispersion of polymerizable silane-modified colloidal silica particles.

(Note 9) TINUVIN 928: Trade name, manufactured by Ciba Specialty Chemicals, Inc., UV absorber (Note 10) TINUVIN 479: Trade name, manufactured by Ciba Specialty Chemicals, Inc., UV absorber (Note 11) ADK STAB LA82: Trade name, manufactured by ADEKA Corporation , Light stabilizer.

Examples 1-32 and Comparative Examples 1-15
The undercoat paint composition shown in Table 4 was applied to a polycarbonate resin plate by air spray so that the dry film thickness was 8 μm. Then, after setting for 5 minutes, it heated at 80 degreeC for 30 minutes. Subsequently, after the object to be coated became 50 ° C. or lower, the active energy ray-curable top coating composition shown in Table 4 was applied thereon by air spray so that the dry film thickness was 5 μm. Then, after preheating at 60 degreeC for 5 minute (s), the coating film was hardened by irradiating an active energy ray with the irradiation amount of 4,000 mJ / cm < ² > using the ultrahigh pressure mercury lamp, and each test coating plate was obtained. About each obtained test coating plate, it used for the following evaluation test. The evaluation results are also shown in Table 4.

Examples 33-38 and Comparative Examples 16-17
The undercoating composition shown in Table 5 was air spray-coated on a polycarbonate resin plate so that the dry film thickness was 8 μm. Then, after setting for 5 minutes, it heated at 120 degreeC for 30 minutes. Subsequently, after the object to be coated became 50 ° C. or lower, the active energy ray-curable top coating composition shown in Table 5 was applied thereon by air spray so that the dry film thickness was 5 μm. Then, after preheating at 60 degreeC for 5 minute (s), the coating film was hardened by irradiating an active energy ray with the irradiation amount of 4,000 mJ / cm < ² > using the ultrahigh pressure mercury lamp, and each test coating plate was obtained. About each obtained test coating plate, it used for the following evaluation test. The evaluation results are also shown in Table 5.

(Abrasion resistance)
Each test plate was subjected to a Taber abrasion test (abrasion wheel CF-10F, load 500 g, 500 rotations) in accordance with ASTM D1044. The haze value was measured about the film before and behind a test, the change ((DELTA) H) was calculated | required, and the following reference | standard evaluated.
A: ΔH is less than 15 ○: ΔH is 15 or more and less than 20 Δ: ΔH is 20 or more and less than 30 ×: ΔH is 30 or more.

(Initial adhesion)
According to JIS K 5600-5-6 (1990), make a 100mm 2mm x 2mm goby mesh on the coating until it reaches the base, and stick an adhesive tape on the surface. The number of remaining Goban eyes film was evaluated.
○: Remaining number / total number = 100/100 Δ: Remaining number / total number = 99 to 90/100 ×: Remaining number / total number = 89 or less / 100

(Weatherability)
For each test plate, using a super UV tester (Dainippon Plastic Co., Ltd., W-13 type, accelerated weathering tester), a black panel temperature of 60 ° C., 24 hours ultraviolet irradiation-24 hours water spray cycle conditions are 1 The test was performed up to 40 cycles. Appearance and adhesion were evaluated according to the following criteria. The appearance was evaluated visually, and the adhesion was evaluated by the same method as the initial adhesion.
○: No cracking occurred in the coating film, adhesion was the remaining number / total number = 100/100 Δ: No cracking occurred in the coating film, but the remaining number / number = 99 or less / 100 Pieces ×: Cracks occurred in the coating film

Claims (5)

After forming an undercoating film on the base material using the room temperature curing or thermosetting undercoating composition (I), a silsesquioxane compound having an organic group directly bonded to a silicon atom is formed thereon. A silsesquioxane compound (a) in which at least one of the organic groups directly bonded to the silicon atom is an organic group having a urethane bond and one (meth) acryloyloxy group, and a photopolymerization initiator (b ) Containing an active energy ray-curable top coating composition (II), and forming a top coating film. The multilayer coating film forming method according to claim 1, wherein the organic group having the urethane bond and one (meth) acryloyloxy group in the component (a) is an organic group represented by the following general formula (A).

[In Formula (A), R ¹ represents a hydrogen atom or a methyl group. R ² represents a divalent hydrocarbon group having 1 to 10 carbon atoms. R ³ represents a divalent hydrocarbon group having 1 to 10 carbon atoms. Y is

(In the formula, R ² is the same as above. N represents an integer of 0 to 9).

(Wherein R ⁴ represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 6 carbon atoms), or

(Wherein R ⁵ represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 6 carbon atoms). ] The method for forming a multilayer coating film according to claim 1 or 2, wherein the active energy ray-curable top coating composition (II) further contains a polymerizable unsaturated compound (c). The method for forming a multilayer coating film according to any one of claims 1 to 3, wherein the undercoat coating composition (I) contains an acrylic resin, an ultraviolet absorber and a light stabilizer. The coated article which has the multilayer coating film formed by the method of any one of Claims 1 thru | or 4.