Process for the production of living (co)polymers and use of the (c0)polymers

专利摘要:
An object of the present invention is to produce a (co) polymer by polymerizing a polar unsaturated compound, wherein the (co) polymer having a precisely controlled number average molecular weight and number of produced molecules can be extremely efficiently produced. It is an object of the present invention to provide a polymerization catalyst and to provide a living polymerization (co) polymer obtained by the method for producing the (co) polymer. For this purpose, there is provided a polymerization catalyst composition comprising an organic oxy salt compound and a composition comprising a hydroxycarbonyl compound having at least an alcoholic hydroxyl group and a carbonyl group in the same molecule, and using this polymerization catalyst composition to provide a polarity. It is possible to polymerize an unsaturated compound, and the composition containing the obtained (co) polymer can provide a particularly excellent thermosetting powder coating.
公开号:KR20020063210A
申请号:KR1020027007431
申请日:2001-10-12
公开日:2002-08-01
发明作者:노보리타다히토；후나키카츠히코；시바하라아쯔시；스즈키마코토；미즈타니카즈미；조야마히로미；하라이사오；하야시타카오미；키요노신지；후지요시세츠코；사카야마히로유키；미조구치미츠유키；마츠모토츠요시；히로세요시하루
申请人:미쯔이카가쿠 가부시기가이샤；
IPC主号:

专利说明:

Manufacturing method of living (co) polymer and use of (co) polymer {PROCESS FOR THE PRODUCTION OF LIVING (CO) POLYMERS AND USE OF THE (C0) POLYMERS}
[3] As for the polymerization of polar unsaturated compounds, many studies have been conducted for many years. Among them, in recent years, studies have been conducted on living polymerization catalysts that want to strictly control the molecular weight of the obtained polymer to produce a polymer having a narrower molecular weight distribution. Thus, living radical polymerization, living anion or living coordination anion polymerization have been studied. Various polymerization catalyst systems have been developed (e.g., living radical polymerization catalysts: polymers, Vol. 48, July, 498-501 (1999), living anions and living coordination anion polymerization catalysts: Molecular Experiments Vol. 2, “Synthesis and Reaction of New Polymers (1) —Synthesis of Additive Polymers,” pp. 165–196, Public Publishing Co., Ltd. (1995).
[4] Although many effective living polymerization catalyst systems have been developed so far, most of them can be obtained only from one molecule of polymerization catalyst, that is, stoichiometry, from the viewpoint of "the number of molecules of the produced polymer to the number of molecules of the polymerization catalyst to be used". It is a theoretical polymerization reaction. This stoichiometric living polymerization reaction requires one molecule of polymerization catalyst to produce one molecule of polymer, and it is difficult to say that it is an efficient and effective method from the viewpoint of industrial practicality. On the other hand, since a plurality of polymer molecules are provided from one molecule of the polymerization catalyst, that is, the catalytic living polymerization reaction makes it possible to significantly reduce the concentration of the catalyst component in the produced polymer, the complicated process of catalyst separation is omitted or simplified. It is possible to minimize or minimize the adverse effect on the physical properties of the catalyst component. In addition, this method can be said to be a truly practical method in terms of reducing the environmental load and reducing the catalyst cost. In fact, the polymerization catalyst system of the polar unsaturated compound which is currently put into practical use consists of a very small amount of radical generator (referring to the catalyst described here) and a large amount of chain transfer agent, and the polymerization reaction does not proceed in a living manner, but It is extremely efficient to generate a number of polymer molecules comparable to the number of molecules of the chain transfer agent from radical molecules.
[5] The catalytic living polymerization of polar unsaturated compounds has been described as follows: (1) Polymerization of methacrylic acid esters using alkali metal alkoxide as catalyst and alcohol as chain transfer agent (SN Lewis et, al., Progress in Organic Coating, 12, 1-26 ( 1984)) and (2) polymerization of methacrylic esters and acrylic esters using a quaternary ammonium salt or Lewis acid as a catalyst and silylketene ketal as a chain transfer agent (OW Webster et al., J. Am. Chem. Soc , 105, 5703 (1983), or Reported Molecular Experiments Vol. 2, "Synthesis and Reaction of New Polymers (1)-Synthesis of Additive Polymers," p. 365-386, Public Publications (1995)). It is only known. However, the method of ① is a good polymerization method for producing oligomers having an average molecular weight of 500 to 3,000, but preparing oligomers or (co) polymers having an average molecular weight of 3000 or more by precisely controlling their molecular weight and molecular weight distribution. not possible. In addition, since this method uses alcohol as a chain transfer agent and a polymerization catalyst, the transesterification reaction proceeds together with the polymerization reaction. For this reason, there exists a fault, such as not applicable to the monomer in which a transesterification reaction becomes a problem. In the method of the above method, the silyl keten ketal to be used is expensive and unstable, and there is a problem in the production method and the like, and it has not been brought to practical use.
[6] Moreover, powder coating is mentioned as an important use using the property of the (co) polymer obtained by the method of this invention, and the prior art regarding it is demonstrated.
[7] Conventionally, the coating of an object uses the paint of a solvent type, and the paint which satisfy | filled various requirements was developed and used for the field | area which requires strict quality, such as for automobiles.
[8] In recent years, in the technical field of paints, in terms of domestic or global environmental preservation, improvement of labor safety and hygiene environment, prevention of fire and explosion, resource saving, etc., instead of solvent-based paints (hereinafter, "powder coating") In addition, as the expectation for high functionalization and diversification of powder coatings has increased due to historical or social requests, high-quality coating films comparable to solvent-based coatings are also used for powder coatings. Performance (eg weather resistance, acid resistance ratio, scratch resistance, etc.) has been required. However, although the coating film performance required for powder coating has become strict, it cannot be said that powder coating which fully satisfies such a requirement is commercially available.
[9] As a specific example of the conventional powder coating, an epoxy resin and polyester resin powder coating are mentioned, for example. However, these paints not only have a problem in weather resistance, but also have a problem in resistance to acid rain, which has recently become a problem in particular, and has a problem in fields such as automobile body coating.
[10] For the purpose of eliminating the drawback, Japanese Patent Application Publication No. 48-38617 discloses an acrylic powder coating, which has achieved a significant improvement in weather resistance. Since then, many studies have been made on acrylic powder coatings, but these acrylic powder coatings have not sufficiently satisfied external appearance properties, physical properties, chemical properties, storage stability, especially surface smoothness and blocking properties. In order to improve the surface smoothness, it is most effective to lower the melt viscosity. However, in order to lower the melt viscosity, the glass transition temperature must be lowered, and it was impossible to satisfy both the performance of the surface smoothness and the blocking property by this method.
[11] And in order to make both performance of surface smoothness and blocking property compatible, the thermosetting powder coating composition (WO 96/03464) using the acrylic (co) polymer which reduced the molecular weight distribution is proposed. However, by reducing the molecular weight distribution, both surface smoothness and blocking properties can be achieved. However, in the living polymerization method shown as an example of the method for producing the acrylic (co) polymer used herein, the recoat property derived from the polymerization catalyst used (adhesiveness with the coating for top coating when repainting and repairing) Because of the shortage, the powder coating, especially the top coating, was not fully effective. Moreover, as another manufacture example, the acryl (co) polymer obtained by the radical polymerization method is fractionated, and the acryl (co) polymer of a predetermined molecular weight distribution is illustrated. However, this method is also a method that cannot be said to be practical, such as an increase in cost, since the ratio of the (co) polymer obtained is low and a process for fractionation is required. Various living polymerization methods have been studied as a method of reducing the molecular weight distribution of an acrylic (co) polymer. However, these are also suitably applied to the coating of powder coating, especially the body of a vehicle such as a car, and the parts of a vehicle such as a car, in particular, the coating of the top coat, such as coloring of the (co) polymer, odor, and cost increase. There was no production method and a thermosetting powder coating to provide an acrylic (co) polymer.
[12] An object of the present invention is to provide a method for producing a living (co) polymer effectively and efficiently by catalytically living polymerizing a polar unsaturated compound when polymerizing a polar unsaturated compound to produce a (co) polymer.
[13] Another object of the present invention is to provide a thermosetting powder coating composition (for example, an acrylic thermosetting powder coating composition) having storage stability, appearance characteristics, physical characteristics, and chemical characteristics in view of the problems of the prior art. Having; In particular, painting of body parts of vehicles such as automobiles and parts of vehicles such as automobiles (aluminum wheels, windshield wipers, fillers, door handles, fenders, bonnets, air spoilers, stabilizers, front grills, etc.), in particular, top coating To provide a thermosetting powder coating composition (for example, acrylic thermosetting powder coating composition) suitably applied to the.
[1] The present invention relates to a method for producing a living polymerization (co) polymer by polymerizing a polar unsaturated compound using an organic oxy salt compound as a catalyst. These polymers and copolymers are extremely important polymers as raw materials for polymer materials or functional polymers.
[2] In addition, the present invention relates in particular to a thermosetting powder coating composition, and more particularly, to the present invention, excellent storage stability (blocking resistance, etc.), appearance characteristics (surface smoothness, sunscreen, transparency, etc.), physical properties ( The present invention relates to a thermosetting powder coating composition having hardness, scratch resistance, recoat resistance), chemical properties (weather resistance, acid resistance, solvent resistance, etc.) and capable of imparting a fired coating film suitable for vehicle coating applications.
[14] Disclosure of the Invention
[15] MEANS TO SOLVE THE PROBLEM The present inventors earnestly examined in order to achieve the said objective, and, as a result, the polymerization reaction of the polar unsaturated compound which catalyzes an organic oxy salt compound in the presence of the hydroxycarbonyl compound which has an alcoholic hydroxyl group and a carbonyl group at least in the same molecule is carried out. By carrying out the polymerization reaction, the polymerization reaction has a stoichiometric or catalytic living polymerization property and can control not only the average molecular weight of the obtained (co) polymer but also the number of molecules of the (co) polymer produced. Discovered and completed the present invention.
[16] That is, the present invention, when preparing a (co) polymer by (co) polymerizing a polar unsaturated compound using an organic oxy salt compound as a catalyst, a hydroxycarbonyl compound having at least an alcoholic hydroxyl group and a carbonyl group in the same molecule In the presence of a polymer, it is a method for producing a living (co) polymer, characterized in that the polymerization.
[17] In addition, the present invention, in order to solve the problems of the prior art, as a result of intensive examination, by using the (co) polymer (A), the thermosetting property having excellent storage stability, appearance characteristics, physical characteristics and chemical characteristics The inventors have found that it is possible to provide a powder coating composition (for example, an acrylic thermosetting powder coating composition), and have completed the present invention.
[18] This invention is specified by the matter described in the following [1]-[17].
[19] [1] A living polymerized (co) polymer, characterized in that a polar unsaturated compound is polymerized in the same molecule in the presence of a hydroxycarbonyl compound having at least an alcoholic hydroxyl group and a carbonyl group in the same molecule. Manufacturing method.
[20] [2] The cation forming the organic oxy salt compound is alkali metal cation, tetraalkyl ammonium cation, trialkylsulfonium cation, tetraaryl phosphonium cation, hexaaryl phosphoranilidene ammonium cation or tetra The manufacturing method of said [1] which is kiss {tris (dialkylamino) phosphoranylideneamino} phosphonium cation.
[21] [3] The production method according to the above [1], wherein the cation forming the organic oxy salt compound is tetraalkyl ammonium cation, tetraaryl phosphonium cation or hexaaryl phosphoranilidene ammonium cation.
[22] [4] The anion forming the organic oxy salt compound is an organic oxy anion derived from a monohydric alcohol, an organic oxy anion derived from a monovalent carboxylic acid or an organic oxy anion derived from a polyhydric carboxylic acid ester. The manufacturing method in any one of 1]-[3].
[23] [5] The production method according to any one of [1] to [3], wherein the anion forming the organic oxy salt compound is an organic oxy anion derived from a monovalent alcohol.
[24] [6] The production method according to any one of [1] to [5], wherein the hydroxycarbonyl compound is α-hydroxyketone or α-hydroxycarboxylic acid ester.
[25] [7] A polar unsaturated compound is a compound having a polar functional group and an unsaturated group selected from the group consisting of a carbonyl group, a cyano group and a pyridyl group in the same molecule, and a compound in which these functional groups and the unsaturated group form a conjugated system directly or indirectly. The manufacturing method in any one of said [1]-[6] which is phosphorus.
[26] [8] The above [1], wherein the polar unsaturated compound is (meth) acrylic acid ester, (meth) acrylonitrile, (meth) acrylamide, vinylpyridine, N-substituted maleide, vinyl ketone, or styrene derivative. The manufacturing method in any one of]]-[6].
[27] [9] Monounsaturates of monounsaturated alcohols with acrylic acid or methacrylic acid, with monohydric alcohols or hydroxyl groups of dihydric alcohols protected by ether bonds and acrylic or methacrylic acid Polyhydric esters formed by esterification of all hydroxyl groups of polyalcohols with acrylic acid or methacrylic acid, acrylonitrile, methacrylonitrile, mono (meth) acrylamides of N, N-2 substituted, vinyl or isopropenyl groups The production method according to any one of the above [1] to [6], which is pyridine, N-aromatic substituted maleimide or vinyl ketone substituted with a.
[28] [10] The production method according to any one of [1] to [9], wherein an active hydrogen compound is used as the chain transfer agent.
[29] [11] The chain transfer agent is a (co) poly (alkylene oxide) having a monovalent carboxylic acid ester, a polyhydric carboxylic acid ester, a monohydric alcohol, a polyhydric alcohol, a monovalent thiol, an active hydrogen in the terminal and / or the main chain. (Co) poly {(meth) acrylic acid ester}, (co) poly {(meth) acrylonitrile}, (co) poly ((meth) acrylamide), (co) poly (vinylpyridine) The preparation according to any one of the above [1] to [9], which is a scavenger, (co) poly (N-substituted maleimide), (co) poly (vinyl ketone) or (co) poly (styrene derivative). Way.
[30] [12] The production method according to any one of the above [1] to [11], wherein the copolymer is used in combination of at least two or more polar unsaturated compounds.
[31] [13] Thermosetting comprising a living polymerization (co) polymer obtained by the method according to any one of [1] to [12] and a curing agent component (B) capable of curing the (co) polymer. Powder coating composition.
[32] [14] The thermosetting powder coating composition according to the above [13], wherein the (co) polymer (A) contains an epoxy group.
[33] [15] The thermosetting powder coating composition according to the above [13] or [14], wherein the (co) polymer (A) has a glass transition temperature of 10 to 100 ° C.
[34] [16] the curable composition component (B) capable of curing the (co) polymer,
[35] (b-1) polycarboxylic acids and / or
[36] (b-2) polyhydric carboxylic anhydride
[37] The thermosetting powder coating composition as described in any one of said [13] or [15] which contains the above.
[38] [17] The thermosetting powder coating composition according to any one of [13] to [16], wherein the thermosetting powder coating composition is used for top coating of automobiles.
[39] Best Mode for Carrying Out the Invention
[40] The present invention provides a living polymerization (co) polymer by (co) polymerizing a polar unsaturated compound using an organic oxy salt compound as a catalyst in the presence of a hydroxycarbonyl compound having at least an alcoholic hydroxyl group and a carbonyl group in the same molecule. It is about how to.
[41] In the present specification, "(co) polymer" means homopolymer or copolymer, and "(co) poly (alkylene oxide) s" means homopolymer or copolymer of alkylene oxide.
[42] Examples of the organic oxy salt compound used in the method of the present invention include an anion moiety having a monovalent organic oxyanion structure represented by a form formed by bonding an organic group to an oxygen atom as a whole structure or as a partial structure, and the like. It is a salt compound formed by the cation part which consists of metal cation or organic cation which can neutralize a charge.
[43] The metal cation in the cation forming such an organic oxy salt compound may be any metal cation as long as the object of the present invention is not impaired. Specifically, for example, an alkali metal cation or an alkaline earth metal may be used. Cation etc. are mentioned, As an organic cation, any organic cation may be used, unless the objective of this invention is impaired, Specifically, quaternary ammonium cation, tertiary sulfonium cation, and quaternary phosphonium cation On, phosphoranilidene ammonium cation, phosphoranilideneaminophosphonium cation, and the like.
[44] As quaternary ammonium cation among these organic cations, for example,
[45] Tetramethylammonium ion, tetraethylammonium ion, tetrabutylammonium ion,
[46] Tetrahexyl ammonium ion, tricyclohexyl methyl ammonium ion,
[47] Ammonium ion in which four hydrocarbon groups are bonded to a nitrogen atom such as N, N-dimethylpiperidinium ion or trimethylphenylammonium ion, or
[48] N-methylpyridinium ion, N-tert-butylpyridinium ion, N-methylpyrrolidinium ion,
[49] And nitrogen-based heterocyclic ammonium ions such as N, N'-dimethylimidazolinium ion or N, N'-diisopropylimidazolinium ion.
[50] Next, as the tertiary sulfonium cation, for example, trimethylsulfonium cation,
[51] Triethylsulfonium cation, triisopropylsulfonium cation, tributylsulfonium cation, or phenyldimethylsulfonium cation.
[52] As quaternary phosphonium cation, for example, tetramethyl phosphonium cation,
[53] Tetraethylphosphonium cation, tetrabutylphosphonium cation,
[54] Tetrahexyl phosphonium cation, tetracyclohexyl phosphonium cation,
[55] Tetraphenylphosphonium cation, tetramethoxyphenylphosphonium cation,
[56] Tetra naphthyl phosphonium cation etc. are mentioned.
[57] As phosphoranilidene ammonium cation, for example,
[58] Hexamethylphosphoranylidene ammonium cation, hexaethylphosphoranylidene ammonium cation,
[59] Hexapropylphosphoranylidene ammonium cation, hexabutylphosphoranylidene ammonium cation,
[60] Hexaphenyl phosphoranilidene ammonium cation, hexanaphthyl phosphoranilidene ammonium cation, etc. are mentioned.
[61] As phosphoranilidene amino phosphonium cation, for example,
[62] Tris (dimethylamino) {tris (dimethylamino) phosphoranylideneamino} phosphonium cation,
[63] Tris (diethylamino) {tris (diethylamino) phosphoranylideneamino} phosphonium cation,
[64] Tris (dimethylamino) bis {tris (dimethylamino) phosphoranylideneamino} phosphonium cation,
[65] Dimethylaminotris {tris (dimethylamino) phosphoranylideneamino} phosphonium cation,
[66] Tetrakis {tris (dimethylamino) phosphoranylideneamino} phosphonium cation,
[67] Tetrakis {tris (morpholino) phosphoranylideneamino} phosphonium cation or
[68] Tetrakis {tris (piperazino) phosphoranylideneamino} phosphonium cation and the like.
[69] Among the cations forming such an organic oxy salt compound, preferred examples include alkali metal cations such as lithium cation, sodium cation, potassium cation, cesium cation or rubidium cation,
[70] Tetraalkylammonium ions such as tetramethylammonium ion, tetraethylammonium ion, tetrabutylammonium ion or tetrahexyl ammonium ion,
[71] Trialkylsulfonium cations such as trimethylsulfonium cation, triethylsulfonium cation, triisopropylsulfonium cation or tributylsulfonium cation, tetraphenyl phosphonium cation, and tetramethoxyphenyl phosphonium cation Tetraaryl phosphonium cation, such as ionic or tetranaphthyl phosphonium cation,
[72] Hexaaryl phosphoranylidene ammonium cation, such as hexaphenyl phosphoranilidene ammonium cation or hexanaphthyl phosphoranilidene ammonium cation, or
[73] Tetrakis {tris (dimethylamino) phosphoranylideneamino} phosphonium cation, tetrakis {tris (morpholino) phosphoranilideneamino} phosphonium cation or tetrakis {tris (piperazino) phosphora Tetrakis {tris (dialkylamino) phosphoranylideneamino} phosphonium cation such as nilideneamino} phosphonium cation; As a more preferable cation, tetraalkyl ammonium cation, tetraaryl phosphonium cation, or hexaaryl phosphoranilidene ammonium cation is mentioned.
[74] In addition, as an anion which forms an organic oxy salt compound in this invention, what kind of organic anion may be used as long as the objective of this invention is not impaired. Specific examples include methanol, ethanol, n-propanol, isopropanol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isopentyl alcohol, tert-pentyl alcohol, n-octyl alcohol, lauryl alcohol, Cetyl alcohol, cyclopentanol, cyclohexanol, allyl alcohol, crotyl alcohol, methylvinylcarbinol, benzyl alcohol, 1-phenylethyl alcohol, triphenylcarbinol, cinnamil alcohol or perfluoro-tert-butyl alcohol, etc. Organooxyanions of monohydric alcohols derived from leaving active hydrogen atoms on alcoholic hydroxyl groups as protons;
[75] Ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, 1,4-cyclohexanediol, trimethylol Organooxyanions of polyhydric alcohols obtained by deactivation of active hydrogen atoms on alcoholic hydroxyl groups such as propane, glycerin, diglycerin, pentaerythritol, or dipentaerythritol as protons;
[76] Methyl acetate, ethyl acetate, cyclohexyl propionate, isopropyl butyrate, methyl isobutyrate, t-butyl isobutyrate, hexyl caproate, butyl laurate, methyl stearate, ethyl oleate, methyl phenyl acetate, methyl cyclohexane carboxylate, 1 1 derived from leaving an active hydrogen atom present in the α-carbon phase such as, 2-bis (2-propylcarbonyloxy) ethane or 1,2,3-tris (2-propylcarbonyloxy) propane as a proton Organooxyanions of carboxylic acid esters;
[77] Dimethyl malonate, dimethyl methyl malate, dimethyl succinate, butyl succinate, butyl succinate, methyl adipic acid, ethyl suverate, methyl butanetetracarboxylic acid, 1,2-bis (2-methoxycarbonylethoxy ) Ethane, 1,2-bis (2-ethoxycarbonylpropoxy) ethane, 1,2-bis (2-ethoxycarbonylpropylmercapto) ethane, N, N, N ', N'-tetrakis Polyhydric carboxylic acid ester derived from active hydrogen atoms present on α-carbon such as (2-butoxycarbonylpropyl) ethylenediamine or oligos having a number average molecular weight of 200 to 1,000,000 or poly (methyl methacrylate) as protons Organooxyanion of;
[78] Ketocarboxylic acid esters derived by deactivation of active hydrogen atoms present in α-carbons in carbonyl groups such as ethyl acetoacetic acid, acetoacetic acid cyclopentyl, methyl carbamoyl acetate, ethyl 2-cyclohexylcarbonyl acetate, and butyl benzoyl acetate as protons And organic oxyanions.
[79] Among these anions, organicoxyanions derived from the monohydric alcohols mentioned above, organicoxyanions derived from monovalent carboxylic acid esters or organicoxyanines derived from polyhydric carboxylic acid esters. More preferably, it is an organooxyanion derived from monohydric alcohol.
[80] The organic oxy salt compound used in the method of the present invention may be formed of a combination of these organic oxy anions and the aforementioned metal cation or organic cation, or may be used in combination of two or more organic oxy salt compounds.
[81] The usage-amount of an organic oxy salt compound can be arbitrarily set with the molecular weight of a target (co) polymer, and it can be determined based on calculation formula (1) or (2) mentioned later.
[82] The hydroxycarbonyl compound in the method of the present invention is a compound having at least an alcoholic hydroxyl group and a carbonyl group in the same molecule, and exemplifying these specifically, for example, 1-hydroxy-1,1-dimethyl-2 -Propanone, 1-hydroxy-1,1-dimethyl-3,3,3-trimethyl-2-propanone,
[83] α-hydroxy-α-methylethylcyclohexylketone,
[84] α-hydroxy-α-methyl-α'-methylcyclohexyl ketone, α-hydroxydicyclohexyl ketone, α-hydroxy-α'-methyldicyclohexylketone, α-hydroxy-α-methylphenylketone,
[85] α-hydroxycyclohexylphenyl ketone, benzoin,
[86] α-hydroxy ketones such as α-hydroxy-α and α-diphenylacetophenone;
[87] α-hydroxyacetic acid ethyl, methyl lactate, cyclohexyl lactate,
[88] α-hydroxyacetic acid ethyl, α-hydroxy-iso-butyrate butyl,
[89] α-hydroxy-α-phenylacetic acid methyl,
[90] α-hydroxycarboxylic acid esters such as α-hydroxy-α and α-diphenyl acetate ethyl;
[91] α-hydroxy-N, N-dimethylacetamide,
[92] α-hydroxy-α, α-dimethyl-N, N-dimethylacetamide, α-hydroxy-α, α-diphenyl-N, N-didimethylacetamide,
[93] α-hydroxy-N, N-diethylpropionamide or
[94] (alpha) -hydroxy-N, N-2 substituted amides, such as (alpha)-hydroxy- (alpha)-methyl-N, N- diethyl propionamide, etc. are mentioned. As another example, any hydroxyketone compound may be used as long as the object of the present invention is not impaired, or two or more kinds of hydroxyketone compounds described above may be used together.
[95] Among these compounds, preferably 1-hydroxy-1,1-dimethyl-2-propanone,
[96] 1-hydroxy-1,1-dimethyl-3,3,3-trimethyl-2-propanone,
[97] α-hydroxy-α-methylethylcyclohexylketone,
[98] α-hydroxy-α-methyl-α'-methylcyclohexylketone,
[99] α-hydroxydicyclohexyl ketone, α-hydroxy-α'-methyldicyclohexyl ketone,
[100] α-hydroxy-α-methylphenylketone,
[101] α-hydroxycyclohexylphenyl ketone, benzoin,
[102] α-hydroxy ketones such as α-hydroxy-α and α-diphenylacetophenone;
[103] α-hydroxyacetic acid ethyl, methyl lactate, cyclohexyl lactate,
[104] ethyl α-hydroxybutyrate, butyl α-hydroxyisobutyrate,
[105] α-hydroxy-α-phenylacetic acid methyl, α-hydroxy-α, α-diphenylacetic acid ethyl
[106] Α-hydroxycarboxylic acid esters such as these;
[107] More preferably, for example, α-hydroxyacetone,
[108] 1-hydroxy-1,1-dimethyl-2-propanone,
[109] 1-hydroxy-1,1-dimethyl-3,3,3-trimethyl-2-propanone,
[110] α-hydroxy-α-methylethylcyclohexylketone,
[111] α-hydroxy-α-methylethyl-α'-methylcyclohexylketone,
[112] α-hydroxydicyclohexyl ketone, α-hydroxy-α'-methyldicyclohexyl ketone,
[113] α-hydroxy-α-methylethylphenylketone, α-hydroxycyclohexylphenylketone, benzoin,
[114] (alpha) -hydroxy- (alpha), (alpha)-diphenyl acetophenone etc. are mentioned.
[115] The usage-amount of hydroxy ketone is normally 0.05 mol or more with respect to 1 mol of organic oxy salt compounds, Preferably it is 0.80-1.20 mol, More preferably, it is 0.95-1.05 mol. Excess hydroxyketone acts as a chain transfer agent.
[116] In the present invention, in the presence of a hydroxycarbonyl compound having at least an alcoholic hydroxyl group and a carbonyl group in the same molecule, an organic oxychloride compound is used as a catalyst to carry out living polymerization of a polar unsaturated compound stoichiometrically and catalytically. It is possible. That is, (1) stoichiometric living polymerization can be carried out by contacting and polymerizing an organic oxy salt compound and a polar unsaturated compound in the presence of a hydroxycarbonyl compound having at least an alcoholic hydroxyl group and a carbonyl group in the same molecule, and (2) catalytic living. Polymerization can also be performed using an active hydrogen compound as a chain transfer agent. In either case, since the polymerization proceeds in a living manner, the number average molecular weight of the produced (co) polymer and the number of molecules of the produced (co) polymer can be calculated and estimated roughly by the following formula (1) or (2). , MWa in the formula (1) or (2) is the molecular weight of the organooxyanion in the organooxy salt compound; Mb is the mole number of the polar unsaturated compound; Ma is the mole number of the said organooxyanion; MWb is the molecular weight of the polar unsaturated compound; MWc is the molecular weight of the chain transfer agent; Mc represents the number of moles of the chain transfer agent.
[117] (Co) polymers obtained by stoichiometric living polymerization:
[118] <Number average molecular weight> ≒ MWa + (Mb / Ma) × MWb (1)
[119] <Number of molecules of (co) polymer produced> ≒ (Number of molecules of the above organic oxy salt compound)
[120] (Co) polymers obtained by catalytic living polymerization:
[121] <Number average molecular weight> ≒ (MWa × Ma + MWc × Mc + Mb × MWb) / (Ma + Mc) (2)
[122] <Number of molecules of (co) polymer produced> ≒ (Number of molecules of the above organic oxy salt compound + number of molecules of the chain transfer agent)
[123] As can be seen from the above formula, according to the method of the present invention, the number-average is arbitrarily adjusted by appropriately adjusting the molecular weight and the number of moles used thereof of the organic oxy salt compound, the polar unsaturated compound or the chain transfer agent to be used, ie the active hydrogen compound. It is possible to manufacture the (co) polymer which controlled the molecular weight and the number of molecules of the produced (co) polymer.
[124] Herein, the unsaturated group in the method of the present invention is a monovalent to tetravalent unsaturated group derived from alkene, and the polar unsaturated compound is a same molecule having a polar functional group and an unsaturated group selected from the group consisting of a carbonyl group, a cyano group and a pyridyl group It is a compound which has both inside, and is a compound in which both form the conjugated system directly or indirectly.
[125] As these compounds, it is (1) (meth) acrylic acid ester, (2) (meth) acrylonitrile, (3) (meth) acrylamide, (4) vinylpyridine, (5) N, for example. -Substituted maleimide, (6) vinyl ketone, or a styrene derivative. In addition, any polar unsaturated compound may be used as long as anionic polymerization is possible by the method of the present invention.
[126] As a specific example, (1) (meth) acrylic acid ester is mentioned ester of acrylic acid or methacrylic acid. As these esters, for example,
[127] (1) -① Monoesters formed by esterification of monohydric alcohols with acrylic acid or methacrylic acid: As these esters, for example, methyl acrylate,
[128] Methyl methacrylate, ethyl acrylate, propyl acrylate, butyl acrylate,
[129] 2-ethylhexyl methacrylate, lauryl acrylate, stearyl methacrylate,
[130] 1,1,1,3,3,3-hexafluoroisopropylacrylate,
[131] 1,1,1,3,3,3-hexafluoroisopropylmethacrylate,
[132] 2,2,2-trifluoroethyl acrylate, 2,2,2-trifluoroethyl methacrylate,
[133] 1H, 1H, 2H, 2H-heptadecafluorodecylacrylate, allyl acrylate,
[134] Allyl methacrylate, cyclohexyl methacrylate, isoponyl acrylate,
[135] Glycidyl acrylate, glycidyl methacrylate,
[136] Tetrahydrofurfuryl acrylate, benzyl acrylate or
[137] (beta) -phenylethyl methacrylate etc. are mentioned.
[138] (1) -② Monoesters formed by esterification of dihydric alcohols having one end protected by an ether bond with acrylic acid or methacrylic acid: As these esters, for example, 2-methoxyethyl acrylate, 2 Ethoxyethyl methacrylate,
[139] 2-phenoxyethyl acrylate, 2-dicyclopentenyloxyethyl acrylate,
[140] 1-methoxy-2-propylmethacrylate, 3-methoxypropylacrylate,
[141] 4-ethoxybutyl methacrylate, 6-methoxyhexamethyl acrylate,
[142] Methoxydiethylene glycol acrylate, phenoxydipropylene glycol methacrylate,
[143] Ethoxytripropylene glycol methacrylate, ethoxy polyethylene glycol acrylate
[144] Or methoxy polypropylene glycol methacrylate.
[145] (1) -③ Polyhydric ester formed by esterification of all hydroxyl groups of acrylic acid or methacrylic acid of the bivalent or more polyhydric alcohols which have two or more hydroxyl groups: As these ester, For example, ethylene glycol diacrylate,
[146] Ethylene glycol dimethacrylate, propylene glycol diacrylate,
[147] Propylene glycol dimethacrylate, 1,3-propanediol dimethacrylate,
[148] 1,4-butanedioldiacrylate, 1,6-hexanedioldimethacrylate,
[149] Neopentyl glycol diacrylate, neopentyl glycol dimethacrylate,
[150] Diethylene glycol diacrylate, dipropylene glycol dimethacrylate,
[151] Triethylene glycol dimethacrylate, tripropylene glycol diacrylate,
[152] Polyethylene glycol diacrylate, polypropylene glycol diacrylate or
[153] Polypropylene glycol dimethacrylate, etc.
[154] In addition, glycerin triacrylate, glycerin trimethacrylate,
[155] Pentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate,
[156] Trimethylolpropanetriacrylate,
[157] Poly (ethylene oxide) triol triacrylate,
[158] Poly (propyleneoxide) trioltriacrylate or
[159] Poly (propylene oxide) triol trimethacrylate etc. are mentioned.
[160] (1)-(4) esters formed by esterification of alcohols containing an ester bond with acrylic acid or methacrylic acid: as these esters, for example,
[161] 2-benzoyloxyethyl acrylate, 2-benzoyloxyethyl methacrylate,
[162] 2-acetyloxyacrylate,
[163] 5-tetrahydrofurfuryloxycarbonylpentyl acrylate,
[164] 5-tetrahydrofurfuryloxycarbonylpentyl methacrylate,
[165] 2,2,6,6-tetramethyl-4-oxy-5-oxa-heptane-1,7-diyl- diacrylate etc. are mentioned.
[166] (1)-(5) esters formed by esterification of alcohols having a cycloacetal bond with acrylic acid or methacrylic acid: as these esters, for example, 2-t-butyl-1,3-dioxycyclopentane- 2'-yl methacrylate or 2-t-butyl-5-ethyl-5-vinylcarbonyloxymethyl-1,3-dioxycyclohexane-2 '(2) -yl acrylate, and the like.
[167] (1) -6-Esters formed by esterification of oxysuccinimide with acrylic acid or methacrylic acid: As these esters, for example, N-oxysuccinimide acrylate or N-oxysuccinimamide methacrylate Etc. can be mentioned.
[168] Esters formed by esterification of alcohols having (1) -⑦ secondary amino groups with acrylic acid or methacrylic acid: examples of these esters include 2-dimethylaminoethyl acrylate or 2-ethylpropylaminoethyl meth Acrylate etc. are mentioned.
[169] (1) -8 esters formed by esterification of alcohols having cyano groups with acrylic acid or methacrylic acid: As these esters, for example, 2-cyanoethyl acrylate or 2-cyanopropyl methacrylate Etc. can be mentioned.
[170] (2) As (meth) acrylonitrile, an acrylonitrile or methacrylate is mentioned, for example.
[171] (3) As (meth) acrylamide, (meth) acrylamide of acrylamide, N-1 substituted, or N, N-2 substituted is mentioned, for example, Acrylamide is illustrated as one of these compounds. can do.
[172] (3)-(1) N-1 substituted (meth) acrylamides: As these compounds, N-methyl acrylamide, N-ethyl acrylamide, N-propyl acrylamide,
[173] N-butyl acrylamide, N-octyl acrylamide, N-phenyl acrylamide,
[174] N-glycidyl acrylamide, N, N'- ethylene bisacrylamide, etc. are mentioned.
[175] (3) -② N, N-2 substituted mono (meth) acrylamides: As these compounds, for example, N, N-dimethylacrylamide, N-ethyl-N-methylacrylamide,
[176] N, N-diethylacrylamide, N, N-di-n-propylacrylamide, N, N-dioctylacrylamide, N, N-diphenylacrylamide, N-ethyl-N-glycidylacrylamide ,
[177] N, N-diglycidyl acrylamide, N-methyl-N- (4-glycidyloxybutyl) acrylamide,
[178] N-methyl-N- (5-glycidyloxypentyl) acrylamide,
[179] N-methyl-N- (6-glycidyloxyhexyl) acrylamide, N-acryloylpyrrolidine,
[180] N-acryloyl-L-pyrrolinemethyl ester, N-acryloyl piperidine,
[181] N-acryloyl morpholine, N-acryloyl imidazole, etc. are mentioned.
[182] (3) -③ N, N'-2 substituted bis (meth) acrylamides: As these compounds, it is N, N'-diethyl-N, N'-ethylenebisacrylamide, N, N ', for example. -Dimethyl-N, N'-hexamethylenebisacrylamide, (N, N'-ethylene) bisacrylamide, etc. are mentioned.
[183] (4) As vinylpyridine, vinyl or isopropenyl substituted pyridine, such as 2-vinylpyridine, 2-isopropenylpyridine, or 4-vinylpyridine, is mentioned, for example.
[184] (5) N-substituted maleimides: As these compounds, for example,
[185] (5) -① N-aliphatic substituted maleimide: As these compounds, N-methyl maleimide, N-ethyl maleimide, etc. are mentioned, for example.
[186] (5) -② N-aromatic substituted maleimide: As these compounds, N-phenyl maleimide, N- (4-methylphenyl) maleimide, etc. are mentioned, for example.
[187] (6) Vinyl ketones: As these compounds, methyl vinyl ketone, isopropenyl methyl ketone, ethyl vinyl ketone, ethyl isopropenyl ketone, butyl vinyl ketone, or phenyl vinyl ketone etc. are mentioned, for example.
[188] (7) Styrene derivatives: As these compounds, p-methoxycarbonyl styrene, p-t-butoxycarbonyl styrene, p-cyano styrene, etc. are mentioned, for example. These polar unsaturated compounds may have substituents other than those described above as long as they do not inhibit the method of the present invention.
[189] Among these unsaturated compounds, preferred ones are, for example,
[190] (1) -① Monoesters formed by esterification of monohydric alcohols with acrylic acid or methacrylic acid: As these esters, for example, methyl acrylate,
[191] Methyl methacrylate, ethyl acrylate, propyl acrylate, butyl acrylate,
[192] 2-ethylhexyl methacrylate, lauryl acrylate, stearyl methacrylate,
[193] 1,1,1,3,3,3-hexafluoroisopropylacrylate,
[194] 1,1,1,3,3,3-hexafluoroisopropylmethacrylate,
[195] 2,2,2-trifluoroethyl acrylate, 2,2,2-trifluoroethyl methacrylate,
[196] 1H, 1H, 2H, 2H-heptadecafluorodecylacrylate, allyl acrylate,
[197] Allyl methacrylate, cyclohexyl methacrylate, isoponyl acrylate,
[198] Glycidyl acrylate, glycidyl methacrylate,
[199] Tetrahydrofurfuryl acrylate, benzyl acrylate or
[200] (beta) -phenylethyl methacrylate etc. are mentioned.
[201] (1) -② Monoesters formed by esterification of dihydric alcohols having one end protected by an ether bond with acrylic acid or methacrylic acid: As these esters, for example, 2-methoxyethyl acrylate, 2 Ethoxyethyl methacrylate,
[202] 2-phenoxyethyl acrylate, 2-dicyclopentenyloxyethyl acrylate,
[203] 1-methoxy-2-propylmethacrylate, 3-methoxypropylacrylate,
[204] 4-ethoxybutyl methacrylate, 6-methoxyhexyl acrylate,
[205] Methoxydiethylene glycol acrylate, phenoxydipropylene glycol methacrylate,
[206] Ethoxytripropylene glycol methacrylate, ethoxy polyethylene glycol acrylate
[207] Or methoxy polypropylene glycol methacrylate.
[208] (1) -③ Polyhydric esters formed by esterification of all the hydroxyl groups and acrylic acid or methacrylic acid of bivalent or more polyhydric alcohols having two or more hydroxyl groups: As these esters, For example, ethylene glycol diacrylate,
[209] Ethylene glycol dimethacrylate, propylene glycol diacrylate,
[210] Propylene glycol dimethacrylate, 1,3-propanediol dimethacrylate,
[211] 1,4-butanedioldiacrylate, 1,6-hexanedioldimethacrylate,
[212] Neopentyl glycol diacrylate, neopentyl glycol dimethacrylate,
[213] Diethylene glycol diacrylate, dipropylene glycol dimethacrylate,
[214] Triethylene glycol dimethacrylate, tripropylene glycol diacrylate,
[215] Polyethylene glycol diacrylate, polypropylene glycol diacrylate or
[216] Polypropylene glycol dimethacrylate, etc.
[217] In addition, glycerin triacrylate, glycerin trimethacrylate,
[218] Pentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate,
[219] Trimethylolpropanetriacrylate,
[220] Poly (ethylene oxide) triol triacrylate,
[221] Poly (propyleneoxide) trioltriacrylate or
[222] Poly (propylene oxide) triol trimethacrylate etc. are mentioned.
[223] (2) acrylonitrile or methacrylonitrile.
[224] (3) -② N, N-2 substituted mono (meth) acrylamides: As these compounds, for example, N, N-dimethylacrylamide, N-ethyl-N-methacrylamide, N, N-di Ethyl acrylamide,
[225] N, N-di-n-propylacrylamide, N, N-dioctylacrylamide, N, N-diphenylacrylamide,
[226] N-ethyl-N-glycidyl acrylamide, N, N- diglycidyl acrylamide,
[227] N-methyl-N- (4-glycidyloxybutyl) acrylamide,
[228] N-methyl-N- (5-glycidyloxypentyl) acrylamide,
[229] N-methyl-N- (6-glycidyloxyhexyl) acrylamide, N-acryloylpyrrolidine,
[230] N-acryloyl-L-pyrrolinemethyl ester, N-acryloyl piperidine,
[231] N-acryloyl morpholine, N-acryloyl imidazole, etc. are mentioned.
[232] (4) Vinyl or isopropenyl-substituted pyridines: As these compounds, 2-vinylpyridine, 2-isopropenyl pyridine, 4-vinylpyridine, etc. are mentioned, for example.
[233] (5) -② N-aromatic substituted maleimide: As these compounds, N-phenyl maleimide, N- (4-methylphenyl) maleimide, etc. are mentioned, for example.
[234] (6) Vinyl ketones: As these compounds, methyl vinyl ketone, isopropenyl methyl ketone, ethyl vinyl ketone, ethyl isopropenyl ketone, butyl vinyl ketone, or phenyl vinyl ketone etc. are mentioned, for example.
[235] As a more preferable polar unsaturated compound, for example,
[236] (1) -monoesters formed by esterification of monohydric alcohols with acrylic acid or methacrylic acid;
[237] Monoesters formed by esterification of dihydric alcohols having one end of (1) -② protected by an ether bond with acrylic acid or methacrylic acid;
[238] (1) -③ Polyhydric esters formed by esterification of the total hydroxyl group and acrylic acid or methacrylic acid of the bivalent or more polyhydric alcohols which have two or more hydroxyl groups;
[239] (2) acrylonitrile or methacrylonitrile;
[240] (3) -② N, N-2 substituted mono (meth) acrylamides are mentioned.
[241] In this invention, you may use a polar unsaturated compound individually or in combination of 2 or more types.
[242] When using a some compound together, the method of using simultaneously, the method of using sequentially, the method of performing a sequence repeatedly, etc. may be taken. When several monomers are used together and superposed | polymerized simultaneously, the copolymer with high randomness is obtained according to the reactivity of these compounds, and the block polymer containing two or more types of blocks is obtained. By repeating simultaneous and sequential polymerization, more complex copolymers are obtained.
[243] In the present invention, an active hydrogen compound is used as the chain transfer agent when performing catalytic living polymerization.
[244] Such active hydrogen compounds include active hydrogen compounds having active hydrogens on carbon atoms, active hydrogen compounds having active hydrogens on oxygen atoms, or active hydrogen compounds having active hydrogens on sulfur atoms. In addition, any active hydrogen compound may be used as long as it does not inhibit the method of the present invention.
[245] Specific examples of the active hydrogen compound having active hydrogen on the carbon atom include, for example, ethyl acetate, cyclohexyl propionate, isopropyl acetate,
[246] Methyl isobutyrate, t-butyl isobutyrate, hexyl caproate, butyl laurate,
[247] Methyl stearate, ethyl oleate, methyl phenyl acetate, methyl cyclohexanecarboxylate,
[248] 1,2-bis (2-propylcarbonyloxy) ethane or
[249] Monovalent carboxylic acid esters such as 1,2,3-tris (2-propylcarbonyloxy) propane;
[250] Dimethyl malonic acid, dimethyl methyl malonic acid, diethyl succinate, butyl 2,3-dimethyl succinate,
[251] Methyl adipic acid, ethyl suverate, methyl butanetetracarboxylic acid,
[252] 1,2-bis (2-methoxycarbonylethoxy) ethane,
[253] 1,2-bis (2-ethoxycarbonylpropoxy) ethane,
[254] 1,2-bis (2-ethoxycarbonylpropylmercapto) ethane,
[255] Polyhydric carboxylic acid esters such as N, N, N ', N'-tetrakis (2-butoxycarbonylpropyl) ethylenediamine;
[256] Ethyl acetoacetic acid, acetoacetic acid cyclopentyl, carbamoyl acetate methyl,
[257] Ketocarboxylic acid esters such as 2-cyclohexylcarbonyl acetate ethyl or benzoyl acetate butyl;
[258] Acetonitrile, 2-cyanopropane, malononitrile, methylmalononitrile,
[259] Nitriles such as 1,3-dicyanopropane or adiponitrile;
[260] Acetone, methyl ethyl ketone, diisopropyl ketone, dicyclohexyl ketone, acetophenone or
[261] Ketones, such as isopropyl phenyl ketone, etc. are mentioned.
[262] Specific examples of the active hydrogen compound having active hydrogen on the oxygen atom include methanol,
[263] Ethanol, n-propanol, isopropanol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol,
[264] Isopentyl alcohol, tert-pentyl alcohol, n-octyl alcohol, lauryl alcohol, cetyl alcohol, cyclopentanol,
[265] Cyclohexanol, allyl alcohol, crotyl alcohol, methylvinylcarbinol, benzyl alcohol,
[266] 1-phenylethyl alcohol, triphenylcarbinol, cinnamil alcohol, perfluoro-tert-butyl alcohol,
[267] α-hydroxyisopropylphenyl ketone, α-hydroxycyclohexylphenyl ketone or
[268] monohydric alcohols such as α-hydroxyisobutyrate methyl;
[269] Ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol,
[270] 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol,
[271] Polyhydric alcohols such as 1,4-cyclohexanediol, trimethylolpropane, glycerin, diglycerin, pentaerythritol or dipentaerythritol;
[272] Aromatic hydroxy compounds, such as a phenol, cresol, xylenol, 2-naphthol, 2, 6- dihydroxy naphthalene, or bisphenol A, etc. are mentioned.
[273] Specific examples of the active hydrogen compound having active hydrogen on the nitrogen atom include methylamine,
[274] Ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine,
[275] sec-butylamine, tert-butylamine, cyclohexylamine, benzylamine, β-phenylethylamine,
[276] Aliphatic or aromatic primary amines such as aniline, o-toluidine, m-toluidine or p-toluidine;
[277] Dimethylamine, methylethylamine, diethylamine, di-n-propylamine, ethyl-n-butylamine,
[278] Aliphatic or aromatic secondary amines such as methyl-sec-butylamine, dipentylamine, dicyclohexylamine, N-methylaniline or diphenylamine;
[279] Ethylenediamine, di (2-aminoethyl) amine, hexamethylenediamine,
[280] 4,4'-diaminodiphenylmethane, tri (2-aminoethyl) amine,
[281] Polyhydric amines having primary or secondary amino groups such as N, N'-dimethylethylenediamine, N, N'-diethylethylenediamine or (2-methylaminoethyl) amine;
[282] Saturated cyclic secondary amines such as pyrrolidine, piperidine, morpholine or 1,2,3,4-tetrahydroquinone;
[283] Unsaturated cyclic secondary amines such as 3-pyrroline, pyrrole, indole, carbazole, imidazole, pyrazole or purine;
[284] Polyhydric amines containing secondary amino groups such as piperazine, pyrazine or 1,4,7-triazacyclononane;
[285] Unsubstituted or N-1 substituted acid amides such as acetoamide, propionamide, N-methylpropionamide, N-methylbenzoic acid amide or N-ethylstearic acid amide;
[286] cyclic amides such as β-propiolactam, 2-pyrrolidone, δ-valerolactam or ε-caprolactam; Dicarboxylic acids, such as succinimide, maleimide, or phthalimide, etc. are mentioned.
[287] Examples of the active hydrogen compound having active hydrogen on a sulfur atom include methanethiol, ethanethiol, n-butanethiol, t-butanethiol, hexanethiol, decanthiol, cyclopentyl mercaptan or
[288] Monovalent thiols such as cyclohexyl mercaptan;
[289] 1,2-ethanedithiol, 1,3-propanedithiol, 2,3-butanedithiol, 1,6-hexanedithiol,
[290] Polyhydric thiols such as 1,2,3-propanetriol or 2,3-di (mercaptomethyl) -1,4-butanedithiol;
[291] And aromatic mercapto compounds such as thiophenol, o-thiocresol, thionaphthol or 1,2-benzenedithiol.
[292] As an active hydrogen compound, Poly (alkylene oxide) which has active hydrogen at the terminal, such as polyethylene oxide or polypropylene oxide;
[293] (Co) poly {(meth) acrylic acid esters}, (co) poly {(meth) acrylonitrile} s, (co) poly (acrylamides) having active hydrogen in the terminal and / or main chain of the molecule, (Co) poly (vinylpyridine) s, (co) poly (N-substituted maleimides), (co) poly (vinyl ketones) or (co) poly (styrene derivatives), and (co) polyesters And (co) polyamides, (co) polylactides, and (co) polysiloxanes.
[294] The above-mentioned active hydrogen compound acts as a chain transfer agent, but its mechanism is not necessarily clear, but it can be interpreted as follows: The organic anion constituting the organic oxychloride compound is not newly formed by addition to the polar unsaturated compound. Since the equilibrium reaction between the warm and the sites with the active hydrogen atoms proceeds reversibly and extremely fast, the active hydrogens are released as protons from the sites with the active hydrogens, leading to their anions, resulting in polymerization from these sites. It is believed that this is disclosed. The active hydrogen includes a compound having a plurality of active hydrogens, but whether or not the polymerization is initiated from all the sites having active hydrogen or from a part thereof, the degree of dissociation of the active hydrogen and the reactivity of the induced anion And the type of polar unsaturated compound or the type of solvent in use.
[295] These active hydrogen compounds may be used singly or in plural forms.
[296] Among these active hydrogen compounds, Preferably, for example, ethyl acetate,
[297] Cyclohexyl propionate, isopropyl butyrate, methyl isobutyrate,
[298] T-butyl isobutyrate, hexane capronate, butyl laurate, methyl stearate,
[299] Ethyl oleate, methyl phenylacetate, methyl cyclohexanecarboxylic acid,
[300] 1,2-bis (2-propylcarbonyloxy) ethane or
[301] Esters of monovalent carboxylic acids such as 1,2,3-tris (2-propylcarbonyloxy) propane;
[302] Dimethyl malonic acid, dimethyl methyl malonic acid, diethyl succinate, butyl 2,3-dimethyl succinate,
[303] Methyl adipic acid, ethyl suverate, methyl butanetetracarboxylic acid,
[304] 1,2-bis (2-methoxycarbonylethoxy) ethane,
[305] 1,2-bis (2-ethoxycarbonylpropoxy) ethane,
[306] 1,2-bis (2-ethoxycarbonylpropylmercapto) ethane,
[307] Polyhydric carboxylic acid esters such as N, N, N ', N'-tetrakis (2-butoxycarbonylpropyl) ethylenediamine;
[308] Methanol, ethanol, n-propanol, isopropanol, n-butyl alcohol, sec-butyl alcohol,
[309] tert-butyl alcohol, isopentyl alcohol, tert-pentyl alcohol, n-octyl alcohol, lauryl alcohol,
[310] Cetyl alcohol, cyclopentanol, cyclohexanol, allyl alcohol, crotyl alcohol,
[311] Methylvinylcarbinol, benzyl alcohol, 1-phenylethyl alcohol, triphenylcarbinol, cinnamil alcohol,
[312] Perfluoro-tert-butyl alcohol, α-hydroxyisopropylphenyl ketone,
[313] monohydric alcohols such as α-hydroxycyclohexylphenyl ketone or α-hydroxyisobutyrate methyl;
[314] Ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol,
[315] 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol,
[316] Polyhydric alcohols such as 1,4-cyclohexanediol, trimethylolpropane, glycerin, diglycerin, pentaerythritol or dipentaerythritol;
[317] Methanethiol, ethanethiol, n-butanethiol, t-butanethiol, hexanethiol, decanthiol,
[318] Monovalent thiols such as cyclopentyl mercaptan or cyclohexyl mercaptan;
[319] (Co) poly (alkylene oxide) s, (co) poly {(meth) acrylic acid esters}, (co) poly {(meth) acrylonitrile} s, having active hydrogen in the terminal and / or main chain, ( Co) poly (acrylamide), (co) poly (vinyl pyridine), (co) poly (N-substituted maleimide), (co) poly (vinyl ketone) or (co) poly (styrene derivative) And the like.
[320] The mode of polymerization of the present invention is not particularly limited. Usually, after contacting a hydroxyketone compound, or a solution in which it is dissolved in a suitable solvent, and an organic oxy salt compound, a chain transfer agent used in the case of use is added and contacted, followed by polymerization by contacting a polar unsaturated compound. As needed, it can also be performed by the batch method which injects these collectively, or the method of supplying this polar unsaturated compound intermittently or continuously. In the case of obtaining a copolymer, a method of simultaneously, collectively or intermittently supplying a plurality of these polar unsaturated compounds or a method of using a plurality of polar unsaturated compounds sequentially can be taken according to the desired form of the copolymer. have. The amount of the organic oxy salt compound used is not particularly limited, but is usually 1 × 10 ⁻⁷ to 1 × 10 ⁻¹ mole to 1 mole of the polar unsaturated compound, and preferably 1 × 10 ⁻⁴ to 3 × 10 ^{Is in} the range of ^-1 mole. The amount of the hydroxyketone compound used is usually 0.05 mol or more, preferably 0.50 to 1.50 mol, and more preferably 0.95 to 1.05 mol with respect to 1 mol of the organic oxy salt compound. The amount of the chain transfer agent, i.e., the active hydrogen compound, is not constant depending on the molecular weight of the (co) polymer to be produced, but is usually 1 × 10 ⁻⁶ to 5 × 10 ⁻¹ mole with respect to 1 mole of the polar unsaturated compound, preferably Preferably it is the range of 1 * 10 <^-4> -2 * 10 <^-1> moles. The temperature of the polymerization reaction is not constant depending on the type and amount of the organic oxy salt compound, the hydroxyketone compound used, the chain transfer agent when used, and the polar unsaturated compound used, but is usually from -50 ° C to 250 ° C, preferably , -20 ° C to 150 ° C. The pressure of the polymerization reaction is not constant depending on the type and amount of the polar unsaturated compound to be used and the reaction temperature. More preferably, it is 0.1-1.0 Mpa.
[321] The reaction time of the polymerization reaction varies depending on the type and amount of the organic oxy salt compound, the hydroxy ketone compound, the chain transfer agent when used, and the polar unsaturated compound used, but is usually within 50 hours, preferably 0.1 to 24 hours. It's time.
[322] Although a trace amount of a polymerization inhibitor is normally added to this polar unsaturated compound, the polymerization reaction in the method of this invention can also be implemented in presence of the said inhibitor depending on a case.
[323] Although the polymerization reaction in the method of the present invention can be carried out in a molten state of a polar unsaturated compound, an appropriate solvent can also be used if necessary. The liquid may be uniform or suspended in some cases. As these solvents, For example, aliphatic or alicyclic hydrocarbons, such as n-hexane, n-heptane, or cyclohexane; Aromatic hydrocarbons such as benzene, toluene or xylene; Aromatic halides such as chlorobenzene or dichlorobenzene; Ethers such as diethyl ether, diphenyl ether, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, ethylene glycol dimethyl ether or diethylene glycol diethyl ether; Aprotic polar solvents such as dimethylformamide, dimethyl sulfoxide, sulfolane or N, N'-dimethylamidazolidinone. In addition, any solvent may be used as long as it does not inhibit the method of the present invention.
[324] After polymerization, the cation constituting the organic oxy salt compound remains as a pair ion at the growth end of all or part of the produced (co) polymer. In order to stably separate a (co) polymer, inorganic acids, such as hydrochloric acid, a sulfuric acid, or phosphoric acid, or organic acids, such as an acetic acid, propionic acid, benzenesulfonic acid, or paratoluenesulfonic acid, are added, for example, and the said cation is added to these. It is also possible to stop the reaction by converting to a salt of an inorganic acid or an organic acid. After the reaction is stopped, if necessary, the solvent used may be used for the following purpose only by distilling off and drying the solvent. Usually, the reaction solution is delayed, or a solution in which the dried body is dissolved in an appropriate solvent is used. Separation can be carried out by adding to a solvent and precipitating. It is also possible to purify the (co) polymer by repeating the precipitation method.
[325] The third invention obtained by the method of the present invention, that is, a thermosetting powder coating composition composed of the (co) polymer (A) obtained by the method of the present invention will be described below.
[326] As the (co) polymer (A), (co) polymer of the at least one epoxy group-containing polar unsaturated compound obtained by the method according to any one of the above [1] to [12], or the above-mentioned epoxy group-containing polar unsaturated compound and polar unsaturated (Co) polymers with compounds are used.
[327] As the epoxy group-containing polar unsaturated compound, any unsaturated compound containing an epoxy group can be used without particular limitation. Examples thereof include glycidyl methacrylate, glycidyl acrylate, β-methylglycidyl methacrylate, and β-. Epoxy-group-containing unsaturated compounds, such as methylglycidyl acrylate and acryl glycidyl ether, are mentioned, These can be used individually or in combination of 2 or more types.
[328] The polar unsaturated compound which may be copolymerized with the epoxy group-containing polar unsaturated compound is not particularly limited as long as it is a polar unsaturated compound. Examples thereof include acrylic acid esters or methacrylic acid ester monomers having an alkyl or cyclohexyl group having 1 to 14 carbon atoms, For example, methyl-, ethyl-, n-propyl-, isopropyl-, n-butyl-, isobutyl-, n-amyl-, isoamyl-, n-hexyl-, cyclohexyl-, 2-ethylhexyl -Acrylic acid derivatives or methacrylic acid derivatives containing acrylic acid esters or methacrylic acid esters such as octyl-, 2-ethyloctyl-, 2-ethyloctyl-, decyl-, dodecyl- and cyclohexyl; You may use these individually or in mixture of 2 or more types.
[329] As a specific example of a polar unsaturated compound, Aromatic vinyl compounds, such as styrene, (alpha) -methylstyrene, and vinyltoluene; Esters of dicarboxylic acids such as maleic acid and itaconic acid; Halogenated ethylenically unsaturated monomers such as vinyl chloride, vinylidene chloride, vinyl fluoride, monochlorotrifluoroethylene, tetrafluoroethylene, and chloroprene; Nitriles such as acrylonitrile and methacrylonitrile; Vinyl esters such as vinyl acetate and vinyl propionate; Α-olefins such as ethylene, propylene, isoprene, butadiene and α-olefins having 4 to 20 carbon atoms; Alkyl vinyl ethers such as lauryl vinyl ether; And other ethylenically unsaturated monomers such as nitrogen-containing vinyls such as vinylpyrrolidone and 4-vinylpyrrolidone, and these can be used alone or in combination of two or more thereof.
[330] By the process of the present invention, the epoxy group-containing polar unsaturated compound in the (co) polymer (A) is 15 to 100 mol%, preferably 20 to 60 mol% in the total monomers.
[331] The glass transition temperature of the (co) polymer (A) is preferably 10 to 100 ° C, in consideration of the storage stability of the powder coating composition and the surface smoothness of the coating film due to the powder composition fluidity decrease during the firing of the powder coating. Preferably it is 20-70 degreeC. If the glass transition temperature is 10 DEG C or higher, the storage stability is good. Moreover, below 100 degreeC, preferable melt viscosity is obtained and the external appearance characteristic of a coating film is favorable.
[332] In the present invention, the glass transition temperature is robot DSC RDC220 (manufactured by Seiko Senshi Kogyo Co., Ltd.), and it is possible to employ a numerical value measured at −20 ° C. to 120 ° C. at 10 ° C./min. The definition of glass transition temperature is described on page 131 of the Polymer Dictionary (Edited by the Polymer Society, Published by Asakura Bookstore, first edition of 1987).
[333] As the curable composition component (B) capable of curing the (co) polymer (A) used in the thermosetting powder coating composition of the present invention, those which can be cured by reacting with a functional group in the (co) polymer (A) can be used. When this functional group is an epoxy group, it is preferable that it is at least 1 sort (s) of compound chosen from the group which consists of polyhydric carboxylic acid and / or polyhydric carboxylic acid anhydride. This compound is a hardening composition component which reacts with the epoxy group which exists in the molecule | numerator of the resin composition for powder coatings of this invention.
[334] As the polyhydric carboxylic acid compound, any compound of aliphatic, aromatic and alicyclic can be used. As an example of aromatic polyhydric carboxylic acid, an isophthalic acid, trimellitic acid, etc. are mentioned, for example, These can be used individually or in combination. As a specific example of alicyclic polyhydric carboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, etc. are mentioned, for example, These can be used individually or in combination. Moreover, polyester resin etc. which have a carboxyl group can also be used. However, in the present invention, it is preferable to use an aliphatic polyhydric carboxylic acid compound in view of coating film properties such as surface smoothness and weather resistance.
[335] The aliphatic polyhydric carboxylic acid (b-1) is not particularly limited as long as the aliphatic polycarboxylic acid (b-1) is substantially an aliphatic compound having at least two carboxyl groups in the molecule, and one or two or more kinds thereof can be used.
[336] Aliphatic dicarboxylic acid etc. are mentioned as a specific example of aliphatic polyhydric carboxylic acid (b-1). As a specific example of aliphatic polyhydric carboxylic acid, for example, succinic acid, glutaric acid, adipic acid, pimelic acid, suveric acid, azelaic acid, sebacic acid, undecane diacid, dodecane diacid, buracic acid, octadecane 2 And about 4 to 24 carbon atoms such as acid, eicosane diacid and dodecane diacid. Among these, dodeca diacid is preferable, and these can be used alone or in combination.
[337] The polyhydric carboxylic acid anhydride (b-2) in this invention contains the aliphatic acid anhydride of an oligomer or a polymer more than linear dimer which has or may not have a carboxyl group in a molecule | numerator substantially, and exists in a molecule | numerator substantially The compound having at least two carboxyl groups and / or acid anhydride groups is not particularly limited, and one or two or more kinds of polyvalent carboxylic acid anhydrides can be used. As an example of polyhydric carboxylic acid anhydride, the dehydration condensate of polyhydric carboxylic acid (b-1) is mentioned. Of these, linear condensed anhydrides of dodecane diacid are preferred, and representative examples thereof are Additol XVL1381 (manufactured by Sorcia). It is preferable to adjust polyhydric carboxylic anhydride (b-2) so that melting | fusing point exists in the range of 40-150 degreeC.
[338] In the method of this invention, the various additives normally added to paint are added. According to the purpose, the thermosetting powder coating composition of the present invention is suitably mixed with a synthetic resin composition containing epoxy resin, polyester resin, polyamide, etc., natural resin or semi-synthetic resin composition containing fibrin or fibrin derivative, etc. Or it is possible to improve coating properties.
[339] According to the purpose, the thermosetting powder coating composition of the present invention is suitably a curing catalyst, a pigment, a flow regulator, a thixotropic agent (thixotropy regulator), a charge regulator, a surface regulator, a glossing agent, an antiblocking agent, a plasticizer, an ultraviolet absorber, and blowing. You may mix | blend additives, such as a blowing agent and a slip agent. Moreover, when using as a clear coat, a small amount of pigment may be mix | blended and may be colored to the extent that complete concealability is not expressed.
[340] The mixing temperature at the time of mechanically kneading the composition containing the (co) polymer (A) and the component (B) is not particularly limited as long as it can prepare a substantially uniform powder coating composition. As the melt kneading apparatus, a heating roller, a heating kneader, an extruder (extruder) or the like is usually used.
[341] As a specific example of the method of mix | blending the thermosetting powder coating composition of this invention, the kneading machine and blenders, such as a roller, a kneader, a mixer (banbury type, a transfer type, etc.), a calender installation, an extruder, are combined suitably, and the conditions of each process are carried out. (Temperature, melting or non-melting, rotational speed, vacuum atmosphere, inert gas atmosphere, etc.) is appropriately set and mixed sufficiently uniformly, and then the powder coating composition in a uniform fine powder state is pulverized by a pulverizing apparatus. Although it is possible to employ | adopt the method of obtaining, it is not limited to these.
[342] The lump-like paint obtained by kneading is pulverized so that it may become about 10-90 micrometers of average particle diameters after cooling. Hammer mill etc. are mentioned as a grinder used.
[343] The thermosetting powder coating composition obtained by pulverization attaches the powder of the thermosetting powder coating composition to a coating object by heating, such as an electrostatic coating method or a fluid immersion method, and heats and heats it to form a coating film. In the case of firing the thermosetting powder coating composition of the present invention, the temperature is usually about 100 ° C. to about 180 ° C., more preferably, about 120 ° C. to about 160 ° C., for about 10 minutes to about 60 minutes. By this, it is possible to perform a crosslinking reaction between the (co) polymer (A) and the curing agent component (B). After firing, it is possible to cool to room temperature to obtain a coating film having excellent characteristics.
[344] In addition, when the thermosetting powder coating composition of the present invention is used as a top coating paint, not only conventional solvent-based paints but also water-based paints are used as the undercoat paints. Likewise, the paint of the present invention has excellent properties.
[345] That is, after coating an aqueous undercoat paint (including pigment and / or metal powder) and drying for a predetermined time, the thermosetting powder coating composition of the present invention is attached to the undercoat paint by the above method. It is made to heat and thermoset by heating, and a coating film is formed.
[346] The coating method of the thermosetting powder coating composition according to the present invention can also be used for automobile bodies or automobile parts (aluminum wheels, windshield wipers or center fillers).
[347] The coating film formed by a suitable or well-known public coating method has excellent storage stability (blocking resistance), appearance characteristics (surface smoothness, screening, transparency, etc.), physical properties (hardness, scratch resistance, top coat adhesion, etc.). It has excellent performance in terms of chemical properties (weather resistance, acid resistance, solvent resistance, etc.).
[348] Hereinafter, the present invention will be described in more detail with reference to Examples, but these are not intended to be limiting and should be understood as illustrative only.
[349] Example 1
[350] After drying the 300 ml flask equipped with the stirrer, the dropping funnel and the temperature measuring tube sufficiently, 2-hydroxy-2,4,4-trimethyl-3-pentanone (169 mg, 1.17 mmol) was precisely placed in the flask. After weighing the mixture, tetrahydrofuran (hereinafter, abbreviated as "THF") solution (11.7 ml, 1.17 mmol) containing tetraphenylphosphonium methoxide (0.10M) was added and stirred to obtain a homogeneous solution. To this solution, n-butanol (87 mg, 1.17 mmol) was added as a chain transfer agent, and THF solution (176 mL, 35.1 g: 351 mmol) of methyl methacrylate (hereinafter abbreviated as "MMA") (2.00 M) was added. MMA) was added dropwise at a rate such that the reaction temperature did not exceed 50 占 폚. It took about 30 minutes to drip. After completion of the dropwise addition, the mixture was stirred for 3 hours, and then THF solution (2.00 ml, 2.00 mmol) of acetic acid (1.0 M) was added to stop the reaction. A trace amount of this reaction mixture was collected and subjected to quantitative analysis by gas chromatography using 1,3,5-trichlorobenzene as an internal standard. Methyl methacrylate and n-butanol were completely consumed. The remaining reaction mixture other than about 0.5 mL used for GPC analysis was injected into methanol (about 2 L). The precipitated solid was separated by filtration, and the solid was washed three times with methanol (40 ml). The obtained solid was dried at 50 degreeC and 10 mmHg for 6 hours, and an unflavored solid (34.2 g) was obtained. The ¹ H-MNR and ¹³ C-NMR spectrum of this solid were almost equivalent to those of poly (methyl methacrylate) manufactured by Aldrich. GPC column (Showa Denko Co., Ltd.) using THF as a developing solvent in a solution in which the remaining reaction mixture (0.5 ml) was diluted with THF until the concentration of poly (methyl methacrylate) therein was about 0.5% by weight. calculated using GPC analysis using poly (methyl methacrylate) as a standard polymer using two columns of shodex-KF-803L and shodex-KF-804L). For the theoretical number average molecular weight of 15,100, the number average molecular weight of the obtained poly (methyl methacrylate) was 14,800, which was in good agreement with the theoretical value. Moreover, the molecular weight distribution index (Mw / Mn) was extremely narrow at 1.11, and it turned out that this polymer is a monodisperse polymer. This result also means that two polymer molecules having similar number average molecular weights are produced for one molecule of catalyst component.
[351] Examples 2-6
[352] In addition, in order to confirm catalytic living polymerization of MMA, polymerization was carried out in the same manner as in Example 1 except that the amount of n-butanol, which is a chain transfer agent used in Example 1, was changed as shown in Table 1 below. In either case, n-butanol and MMA were completely consumed. The GPC analysis result of the obtained poly (methyl methacrylate) is shown in Table 1 with the result of Example 1. The number average molecular weight of the polymer obtained in each example shows almost good agreement with the theoretical number average molecular weight. The deviation of the theoretical number average molecular weight was within 3% of the theoretical number average molecular weight. Moreover, the molecular weight distribution index of the obtained polymer was 1.06-1.18, and it was a monodisperse polymer. These series of results strongly suggest that the polymerization of MMA using an organic oxychloride compound as a catalyst proceeds catalytically in the presence of a hydroxycarbonyl compound having at least an alcoholic hydroxyl group and a carbonyl group in the same molecule. It is shown.
[353] Comparative Example 1
[354] Polymerization was carried out in the same manner as in Example 1 except that 2-hydroxy-2,4,4-trimethyl-3-heptanone used in Example 1 was not used. The consumption rates of n-butanol and MMA were 78% and 100%, respectively. The polymer obtained was a mixture of a polymer having a number average molecular weight of 41,600 and 8,000 and a molecular weight distribution index of 4.61. The results and the results of Example 1 show that the hydroxyketone compound plays an extremely important role because it controls the polymerization reaction.
[355] ExampleUsage amount of n-butanolTheoryGPC analysis result Mn Mw / Mn One1.1715,10014,8001.11 22.3410,1009,9001.18 34.686,0706,0101.16 410.53,0802,9901.09 522.21,5701,6001.09 623.91,1001,0701.06
[356] Note: In the table, Mn represents the number average molecular weight and Mw / Mn represents the molecular weight distribution.
[357] Application Example
[358] In the description of the following examples, "part" and "%" are values based on mass unless otherwise specified.
[359] [Manufacture of Paint]
[360] A white paint of acrylic melamine crosslinked was coated on a 0.8 mm thick bonderite steel sheet subjected to zinc phosphate treatment to a thickness of 20 μm, and then baked at 140 ° C. for 30 minutes to produce a substrate coated steel sheet. It was.
[361] [Performance evaluation]
[362] Performance evaluation was performed as follows.
[363] ① Blocking resistance test of powder coating composition
[364] Powder coating composition (6.0 g) was put in a cylindrical container with an inner diameter of 20 mm, stored at 23 ° C. for 7 days, and then the powder was taken out to observe the blocking degree of the powder coating by visual and finger contact. Evaluated.
[365] ◎: fairly normal
[366] ○: slightly deteriorated
[367] ×: deteriorated
[368] ② Appearance by visual observation (surface smoothness, sunyoungseong)
[369] The coating film appearance was visually determined and evaluated as ◎, 및, and ×.
[370] ◎ particularly excellent
[371] ○: good
[372] ×: defective
[373] ③ Long Wave (Lw)
[374] Lw was measured by Wavescan Plus (manufactured by BYK). This Lw is an index indicating the surface smoothness of the coating film, and the smaller the value of the index, the smoother the surface.
[375] ④ gloss
[376] The value measured with the glossmeter (60 degree gross | gum) was shown.
[377] ⑤ transparency
[378] The color difference ΔE between the coating film to be measured and the substrate coating film was measured by a color guide (manufactured by BYK).
[379] ◎: -0.5 <ΔE <0.5
[380] ×: ΔE ≦ −0.5 or 0.5 ≦ ΔE
[381] ⑥ Hardness test of coating
[382] It evaluated by the pencil hardness test (based on Japanese Industrial Standard JIS K5400 6.14). Marking is indicated by a pencil hardness symbol.
[383] ⑦ Rub Resistance
[384] A friction test was carried out in which the coating film surface was rubbed with a brush using a 3% abrasive suspension, and the glossiness retention rate was calculated by performing a glossiness (20 ° gross) evaluation before and after the friction.
[385] Glossiness retention rate = (20 ° gross after test) / (20 ° gross before test) × 100
[386] Gloss retention was evaluated as ◎, ,, and ×.
[387] ◎: 60% or more
[388] ○: more than 40% less than 60%
[389] ×: less than 40%
[390] ⑧ Recoat
[391] The recoat property test was done by the board | substrate adhesion test based on JISK5400 8.5.2. The number of unpeeled portions was evaluated as ,, ×, and ×.
[392] ◎: 100
[393] ○: more than 80 less than 99
[394] ×: less than 80
[395] ⑨ acid resistance
[396] 10 volume% sulfuric acid solution was dripped at the coating film surface, and it was left to stand at room temperature for 1 day. Thereafter, the sulfuric acid solution was wiped off, and the surface thereof was observed and evaluated as , , And x.
[397] ◎: no trace
[398] ○: very few traces observed
[399] ×: trace was observed
[400] ⑩ solvent resistance
[401] The coating film surface was rubbed 50 times back and forth on the gauze impregnated with xylol, and the surface was observed and evaluated as , , And x.
[402] ◎: no trace
[403] ○: very few traces observed
[404] ×: trace was observed
[405] 후 weather resistance test
[406] A 2,000 hour accelerated test was conducted by QSWOM to measure the glossiness of the coating film before and after the accelerated test, and the gloss residual ratio (%) was calculated by the following equation.
[407] Glossiness remaining ratio = (20 ° gross after promotion test) / (20 ° gross before promotion test) × 100
[408] [Polymer (A) Production Example 1]
[409] The (co) polymer (A) of this invention was evaluated as resin for coatings.
[410] Example 7 (Manufacturing Example 1)
[411] After drying a 10-liter flask equipped with a stirrer, a dropping funnel and a temperature measuring tube sufficiently, it was hydroxyketone compound 1-hydroxycyclohexylphenyl ketone (5.37 g, 26.3 mmol) and an oxy salt at room temperature under nitrogen atmosphere. The potassium salt (5.33 g, 25.1 mmol) of the methylmalonic acid diethyl compound was accurately weighed. 1400 mL of THF was added thereto and stirred to obtain a homogeneous solution. Methyl isobutylate (12.8 g, 126 mmol) was added to this solution as a chain transfer agent. Then the solution was cooled under ice cooling. MMA (1.00M), n-butyl methacrylate (hereinafter abbreviated as "n-BMA", 0.1M), isobutyl methacrylate (hereinafter abbreviated as "i-BMA", 0.1M) And 1256 ml (126 g: 1.26 mol MMA, 17.9 g: 126 mmol n-BMA, 17.9 g: 126 mmol i-) THF solution, each containing glycidyl methacrylate (abbreviated herein as "GMA", 0.8 M). BMA, containing 143 g: 1.00 mmol GMA) was added dropwise at a rate such that the reaction temperature did not exceed 10 占 폚. It took about 2 hours to drip. After completion of the dropwise addition, the mixture was stirred at room temperature for 5 hours, and then 1.0M of acetic acid THF solution (46.5 ml, 46.5 mmol) was added to stop the reaction. The entire monomer was consumed completely. Aluminum silicate (25.6 g) was added to the reaction mixture, which was stirred at room temperature for 2 hours, and this was filtered. The mother liquor was concentrated and solidified, and the obtained solid was dried at 50 ° C and 10 mmHg for 24 hours. 297 g of colorless, odorless solids were obtained. The glass transition temperature of this solid was 35 degreeC, the number average molecular weight of the obtained copolymer was 2,410 and the molecular weight distribution index was 1.34 with respect to the theoretical number average molecular weight 2,138.
[412] [Association Comparative Production Example of (Co) polymer (A)]
[413] 66.7 parts of xylenes were placed in a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen gas introduction tube, and the temperature was raised to the reflux temperature. A polar unsaturated compound (part) as shown in Table 2 below and t-butylperoxy 2-ethylhexanoate (PB-O: manufactured by Nippon Oil Industries, Ltd.) as a polymerization initiator are dissolved therein, and the mixed solution is It was dripped over 5 hours, and after that, it hold | maintained at 100 degreeC for 5 hours. The polymer (comparative manufacture example 1, 2 and 3) was obtained by removing the solvent of the obtained polymer solution. In the following Table 2, the characteristic value of the obtained copolymer was also shown together.
[414] Preparation Example 1 and Comparative Preparation Examples 1, 2, and 3Preparation Example 1Comparative Production Example 1Comparative Production Example 2Comparative Production Example 3 Methyl methacrylate50503535 N-butyl methacrylate5555 Isobutyl methacrylate5555 Glycidyl methacrylate40404040 Styrene--1515 PB-O ^{* 1} -10813 Number average molecular weight (Mn)2410248023001720 Weight average molecular weight (Mw)3220578051503510 Molecular Weight Distribution (Mw / Mn)1.342.332.242.04 Glass transition temperature35353520
[415] * 1: t-butylperoxy 2-ethylhexanoate (made by Nippon Oil Industries, Ltd.)
[416] [Application Examples 1 and 2]
[417] A polymer (A) (production example 1) and a hardening | curing composition component (B) are mix | blended in the ratio (part) shown in the said Table 2, and it is CGL1545 (product of Chiba Chemical Co., Ltd.) with respect to a total of 100 weight part of (A) and (B). , 1.5 parts of UV absorber), 1.5 parts of Chinuvin 144 (manufactured by Chiba-Gaiiki Co., Ltd., light stabilizer), 0.2 parts of benzoin (blowing inhibitor), 0.5 parts of ethylene bis stearoamide (blowing inhibitor and slip agent), and 1.0 part of Regimix RL-4 (flow regulator) was added, and the mixture was melt-molded in a kneader, cooled, and finely pulverized in a grinder to obtain a powder coating. The powder coating thus obtained was coated on an undercoated steel sheet so as to have a film thickness of 40 μm by electrostatic spraying, and then heated at 150 ° C. for 30 minutes to obtain a top coat mill test plate.
[418] Application Examples 1, 2, 3 and 4
[419] A test plate was obtained in the same manner as in Application Example 1, except that the Application Comparative Polymers ((A) Application Comparative Preparation Examples 1, 2, and 3) and (B) were mixed in the proportions (parts) shown in Table 3 below.
[420] [Evaluation Results of Application Examples and Comparative Examples]
[421] The results of evaluation of the powder coating and coating film formed in Application Examples 1 and 2 are shown in Tables 3 and 4 below. Moreover, the result of having evaluated the powder coating and coating film which were formed in the application comparative example 1, 2, 3, and 4 which concerns on this is shown in following Table 3 and Table 4. The powder coating compositions of the examples shown in Table 4 are within the scope of the present invention, and this result shows that the composition of the present invention does not reduce the storage stability (blocking resistance) as compared with the conventional powder coating, and the appearance characteristics (surface) It is a thermosetting powder coating composition that can give a coating film having smoothness, lightness, transparency, etc.), physical properties (hardness, scratch resistance, recoating, etc.), and chemical properties (weather resistance, acid resistance, solvent resistance, etc.). .
[422] Coating composition of Application Examples 1 and 2 and Comparative Examples 1, 2, 3 and 4 Application Example 1Application Example 2Application Example 1Application Example 2Application Example 3Application Example 4 Polymer (A)Preparation Example 176.868.8 Comparative PolymerComparative Production Example 1 76.8 Comparative Production Example 2 76.868.868.8 Curing agent (B)Dodecane 2 Mountain23.2 23.223.2 XVL 1381 ^{* 2} 31.2 31.231.2
[423] * 2: Polycarboxylic anhydride hardener Additol XVL1381 (manufactured by Sorcia)
[424] Evaluation Results in Application Examples and Comparative ExamplesApplication Example 1Application Example 2Application Example 1Application Example 2Application Example 3Application Example 4 Blocking resistance◎◎○○○× Visual appearance◎◎×××○ Long Wave3.41.910.112.18.95.4 Gloss (60 ° gross)919191929292 Transparency◎◎◎◎◎◎ Coating HardnessHHHHHB Scratch resistance◎◎◎◎◎× Recoat◎◎◎◎◎◎ Acid resistance◎◎◎◎◎○ Solvent resistance◎◎◎◎◎× Weather resistance959595939366
[425] As described above, according to the present invention, the hydroxycarbonyl compound is not particularly problematic in terms of manufacturing or handling, and by using together with an inexpensive organic oxy salt compound, the polymerization performance of the organic oxy salt compound with respect to the polar unsaturated compound is remarkably improved. The number average molecular weight of the polymer produced by polymerizing a polar unsaturated compound using an organic oxy salt compound as a catalyst in the presence of a hydroxycarbonyl compound having at least an alcoholic hydroxyl group and a carbonyl group in the same molecule. However, it is possible to produce polymers with precisely controlled number of produced molecules extremely efficiently.
[426] BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to thermosetting powder coating compositions (e.g., acrylic thermosetting powder coating compositions) having storage stability, appearance properties, physical properties, and chemical properties, which have not been achieved in the prior art, in particular, for vehicles such as automobiles. Thermosetting properties suitable for painting of body parts and automobile parts (aluminum wheels, windshield wipers, fillers, door handles, fenders, bonnets, air spoilers, stabilizers, front grills, etc.), especially for top coating It is possible to provide a powder coating composition (for example, an acrylic thermosetting powder coating composition).

权利要求:
Claims (17)
[1" claim-type="Currently amended] A process for producing a living polymerized (co) polymer, comprising using an organic oxy salt compound as a catalyst and polymerizing a polar unsaturated compound in the presence of a hydroxycarbonyl compound having at least an alcoholic hydroxyl group and a carbonyl group in the same molecule.
[2" claim-type="Currently amended] The cation forming the organic oxy salt compound is an alkali metal cation, a tetraalkyl ammonium cation, a trialkylsulfonium cation, a tetraaryl phosphonium cation or a hexaaryl phosphoranylidene ammonium cation. On or tetrakis {tris (dialkylamino) phosphoranylideneamino} phosphonium cation.
[3" claim-type="Currently amended] The living polymerization (co) according to claim 1, wherein the cation forming the organic oxy salt compound is tetraalkyl ammonium cation, tetraaryl phosphonium cation or hexaaryl phosphoranilidene ammonium cation. Method for producing a polymer.
[4" claim-type="Currently amended] The organic anion derived from a monohydric alcohol, an organooxyanion derived from a monovalent carboxylic acid, or a polyvalent carboxylic acid according to any one of claims 1 to 3, wherein the anion forming the organic oxy salt compound is derived. A process for producing living polymerization (co) polymers, characterized in that they are organooxyanions derived from esters.
[5" claim-type="Currently amended] The method for producing a living polymerization (co) polymer according to any one of claims 1 to 3, wherein the anion forming the organic oxy salt compound is an organic oxy anion derived from a monovalent alcohol.
[6" claim-type="Currently amended] The said hydroxycarbonyl compound is (alpha)-hydroxy ketones or (alpha)-hydroxycarboxylic acid ester, The manufacturing method of the living-polymerization (co) polymer of any one of Claims 1-5 characterized by the above-mentioned.
[7" claim-type="Currently amended] The said polar unsaturated compound is a compound which has a polar functional group and an unsaturated group selected from the group which consists of a carbonyl group, a cyano group, and a pyridyl group in the same molecule, The said functional group and the said unsaturated group are in any one of Claims 1-6. A process for producing a living polymerization (co) polymer, wherein the group is a compound which forms a conjugated system directly or indirectly.
[8" claim-type="Currently amended] The said polar unsaturated compound is a (meth) acrylic acid ester, (meth) acrylonitrile, (meth) acrylamide, vinylpyridine, N-substituted maleide of any one of Claims 1-6. And vinyl ketones or styrene derivatives.
[9" claim-type="Currently amended] The polar unsaturated compound according to any one of claims 1 to 6, wherein the polar unsaturated compound comprises monoesters of monohydric alcohols and acrylic acid or methacrylic acid, dihydric alcohols with one end protected by an ether bond, acrylic acid or methacrylic acid, Monoesters, polyhydric esters formed by esterification of all hydroxy groups of polyhydric alcohols having two or more hydroxyl groups with acrylic acid or methacrylic acid, acrylonitrile, methacrylonitrile, N, N-2 substituted mono (Meth) acrylamide, pyridine substituted by vinyl or isopropenyl group, N-aromatic substituted maleimide, or vinyl ketone. The manufacturing method of the living-polymerization (co) polymer characterized by the above-mentioned.
[10" claim-type="Currently amended] The method for producing a living polymerized (co) polymer according to any one of claims 1 to 9, wherein an active hydrogen compound is used as the chain transfer agent.
[11" claim-type="Currently amended] The said chain transfer agent is a monohydric carboxylic acid ester, polyhydric carboxylic acid ester, monovalent alcohol, polyhydric alcohol, monovalent thiol, terminal, and / or active hydrogen in a main chain of any one of Claims 1-9. (Co) poly (alkylene oxide) s, (co) poly {(meth) acrylic acid esters}, (co) poly {(meth) acrylonitrile} s, and (co) poly ((meth) acrylamides) Living), (co) poly (vinylpyridine), (co) poly (N-substituted maleimide), (co) poly (vinyl ketone) or (co) poly (styrene derivative) Method for producing a polymerized (co) polymer.
[12" claim-type="Currently amended] The method for producing a living polymerization (co) polymer according to any one of claims 1 to 11, wherein a copolymer is produced by using at least two polar unsaturated compounds.
[13" claim-type="Currently amended] A living polymerization (co) polymer (A) obtained by the method described in any one of claims 1 to 12,
A thermosetting powder coating composition comprising a curing agent component (B) capable of curing the (co) polymer.
[14" claim-type="Currently amended] The thermosetting powder coating composition according to claim 13, wherein the (co) polymer (A) contains an epoxy group.
[15" claim-type="Currently amended] The thermosetting powder coating composition according to claim 13 or 14, wherein the (co) polymer (A) has a glass transition temperature of 10 to 100 ° C.
[16" claim-type="Currently amended] The curable composition component (B) according to any one of claims 13 to 15, wherein the curable composition (B) capable of curing the (co) polymer is
(b-1) polycarboxylic acids and / or
(b-2) polyhydric carboxylic anhydride
Thermosetting powder coating composition comprising a.
[17" claim-type="Currently amended] 17. The thermosetting powder coating composition according to any one of claims 13 to 16, wherein the thermosetting powder coating composition is used for the top coating of an automobile.

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同族专利:

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公开号 | 公开日

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CN1213073C|2005-08-03|

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US6762259B2|2004-07-13|

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KR20040101547A|2004-12-02|

---

CN1398269A|2003-02-19|

---

US20030023003A1|2003-01-30|

---

KR100507126B1|2005-08-10|

---

JPWO2002030995A1|2004-02-19|

---

EP1266910A1|2002-12-18|

---

KR100476324B1|2005-03-16|

---

EP1266910A4|2004-08-18|

---

WO2002030995A1|2002-04-18|

---

JP3789430B2|2006-06-21|

引用文献:

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公开号 | 申请日 | 公开日 | 申请人 | 专利标题

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法律状态:
2000-10-12|Priority to JPJP-P-2000-00312248

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2000-10-12|Priority to JP2000312248

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2001-10-12|Application filed by 미쯔이카가쿠 가부시기가이샤

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2002-08-01|Publication of KR20020063210A

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2005-03-16|Application granted

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2005-03-16|Publication of KR100476324B1

优先权:

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申请号 | 申请日 | 专利标题

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JPJP-P-2000-00312248|2000-10-12|

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JP2000312248|2000-10-12|