TW201242984A - Polyurethane compound, composition containing the same, aqueous polyurethane dispersion composition and cured product thereof - Google Patents

Abstract

Provided is a novel polyurethane compound capable of providing a cured product with high elasticity, high hardness, a composition containing the same, an aqueous polyurethane dispersion composition and a cured product thereof. The present invention refers to a polyurethane compound, which is obtained by reacting a polycarbonate diol (A) at least containing a repeat unit represented by the following formula (1) and having one hydroxyl group at both ends of the molecular chain, a polyisocyanate compound (B) and a (meth)acrylate compound (C) with one or more hydroxyl groups in the molecule.

Description

201242984 6. Invention: [Technical Field of the Invention] This month: a dispersion of a compound of a polyamine s, a compound containing the above-mentioned polyamine vinegar compound, a compound of the present invention, and the like Hardened material. [Prior Art] Polyamines have been widely used in, for example, aircraft and automobiles, and are used for materials such as walls and flooring, home appliances/electronic materials, or as coatings, coating agents, or The raw material of the agent. The above-mentioned coating film such as a coating or a coating agent is required to have a hardness, a strength, a long-lasting property, and the like, not only for expressing the aesthetics of the appearance but also for ensuring the compliance of the substrate. In order to achieve this (4) (4), it is required to provide a hard coating film of polyamines. The polyamine vinegar compound which is a raw material of such a coating material, a coating agent or an adhesive agent is made into an active energy ray-curable resin in terms of workability and the like. Among them, the acrylic acid modified vinegar resin is rapidly hardened by irradiation with an active energy ray, the processing speed is fast, and the whole cost is low, and various coating agents such as a hard coat agent are used. In a wide range of fields such as coatings and adhesives. On the hard coating agent, there are various functions such as weather resistance, abrasion resistance, heat resistance, hydrolysis resistance, etc., so it has been explored that the functional surface is superior to the polyester modified or polyfluorene-based modified amine. Polycarbonate-based acrylic acid modified amine ester resin of ester resin. For example, a polyester type has a disadvantage that hydrolysis resistance is poor due to an ester bond, and a hard coat film produced using the same has a disadvantage of poor hydrolysis resistance, and a hard coat film produced by the use of a hard coat agent having weather resistance and heat resistance. Poor shortcomings. In Patent Document 1, 'there is a proposal for a composition of 1,6-hexanediol type polycarbonate diol-based resin, which is excellent in abrasion resistance, adhesion, and weather resistance, 324043 4 201242984. However, there is still a problem in the hardness of one of the important functions of the hard coating agent. [PRIOR ART DOCUMENT] [Patent Document 1] JP-A-2002-348499 SUMMARY OF INVENTION [Problem to be Solved by the Invention] An object of the present invention is to provide a hardening having high modulus of elasticity and high hardness. A novel polyurethane compound containing a composition of the compound, an aqueous polyurethane dispersion composition, and a cured product thereof. (Means for Solving the Problems) The present invention is an invention for solving the above problems, and specifically has the following configuration. [1] A polyurethane compound which is a polycarbonate diol (A) having a repeating unit represented by the following formula (1) and having one hydroxyl group at each end of the molecular chain, and a polyisocyanate compound (B) The (meth) acrylate compound (C) having one or more hydroxyl groups in the molecule is obtained by a reaction.

(wherein Z1 and Z2 each independently represent a linear or branched chain of a diene having a carbon number of 1 to 10). [2] The polyurethane compound according to the above [1], wherein the polycarbonate 324043 5 鳙201242984 diol (A) has a repeating unit represented by the formula (1) and a repeating unit represented by the formula (2), and the molecular chain Both ends have one hydroxyl group.

(wherein Z3 represents a linear or branched alkanediyl group having 2 to 10 carbon atoms which may have a substituent, a cycloalkyldiyl group having 3 to 10 carbon atoms which may have a substituent, or may have a substituent Any one of the two groups of the second base having an alicyclic structure having 5 to 10 carbon atoms in the main chain). [3] The polyurethane ester compound according to the above [1] or [2], which is obtained by reacting an acid group-containing polyol (D). [4] The polyurethane compound according to any one of the above [1] to [3] which is obtained by reacting a chain extender (E). [5] An aqueous polyurethane dispersion obtained by dispersing at least the polyamine g compound according to any one of the above [1] to [4] in an aqueous medium. [6] A polyurethane solution obtained by dispersing or dissolving at least the polyurethane compound according to any one of the above [1] to [4] in an organic solvent. [7] A polyamine composition comprising the polyurethane ester compound according to any one of the above [1] to [4], a polymerization initiator (G), and optionally a polymerizable unsaturated bond. Compound (F). [8] A cured product obtained by hardening the polyurethane composition described in the above [7]. [9] An aqueous polyurethane dispersion composition according to any one of the above [1] to [4], wherein the polymerization initiator (G) 324043 6 8 201242984 a is optionally provided The compound (F) having a polymerizable unsaturated bond is dispersed in an aqueous medium. [10] A cured product which is obtained by applying the aqueous polyurethane dispersion composition described in the above [9], drying and hardening. [11] A method for producing a polyurethane compound according to the above [1] or [2], which is to react a polycarbonate diol (A) with a polyisocyanate compound (B) to obtain an isocyanate at the terminal. After the polyurethane prepolymer of the acid group (is〇cyanat〇), the polyurethane prepolymer is reacted with a (mercapto)acrylic acid vinegar compound (c) having one or more groups in the molecule. [12] A method for producing a polyurethane compound according to the above [3], which is a reaction of a polycarbonate diol (A), a polyisocyanate compound (B), and an acid group-containing polyol 〇 () 'After obtaining a polyurethane prepolymer having an isocyanate group at the end, 'the aforementioned polyamine vinegar prepolymer is reacted with a (meth) acrylate compound (C) having one or more hydroxyl groups in the molecule. [13] A method for producing a polyurethane compound according to the above [4], which comprises a polycarbonate diol (A), a polyisocyanate compound (B), and optionally an acidic group-containing polyol (D). After the reaction, a polyurethane prepolymer having an isocyanate group at the end is obtained, and then the chain extender (E) is allowed to react, and then reacted with a (meth) acrylate compound (C) having one or more radicals in the molecule. [14] A method for producing an aqueous polyurethane dispersion according to the above [5], which comprises a polycarbonate (A), a polyisocyanate compound (B), and an acid group-containing polyol ( D) Reaction 'After obtaining a polyamine vinegar prepolymer having an isocyanate group at the end, neutralizing the acidic group derived from the above-mentioned acid group-containing polyol, and dispersing it in an aqueous medium, 'optionally and chain 7 324043 201242984 The elongation agent (E) is reacted, and then reacted with a (mercapto) acrylate compound (C) having one or more hydroxyl groups in the molecule. [15] A method for producing a polyurethane solution according to the above [6], which is a polycarbonate diol (A), a polyisocyanate compound (B), and optionally an acidic group-containing polyol (D) After reacting in an organic solvent to obtain a polyurethane prepolymer having an isocyanate group at the end, it is reacted with a chain extender (E) as needed, and a (mercapto) acrylate compound having one or more hydroxyl groups in the molecule. (C) Reaction. [Effects of the Invention] The polyurethane compound of the present invention, the composition containing the compound, and the cured product thereof have excellent elastic modulus and hardness, and are most suitable for various fields requiring high hardness, and are therefore applicable to metals, wood, paper, and the like. Coatings for plastics, electric/electronics/automotives, automotive interiors and exteriors, coatings for floors and walls of furniture and building materials, various adhesives, inks, decorative films (especially hard coating layers for decorative films), etc. In many fields. [Embodiment] Hereinafter, a polyurethane compound of the present invention, a composition containing the same, and a cured product thereof will be described in detail. (Polycarbonate diol (A)) The polycarbonate diol (A) of the present invention is characterized by having a repeating unit represented by the following formula (1). 324043

8 8 201242984 In the formula (1), Z and Z2 each independently represent a linear or branched alkanediyl group having a carbon number of 丨10. Examples of the alkanediyl group represented by the above 21 and Z2 include an anthracene group, an exoethyl group, a triadenylene group, a propyl group-1,2-diyl group, a tetramethylene group, and a butane-U-diyl group. , Wuya 曱基, 六亚曱基, 七亚曱基, 八亚曱基, 十亚曱基, etc. In order to further increase the modulus of elasticity of the cured product containing the polymerizable composition of the obtained polyurethane compound, the alkanediyl group represented by the above 21 and 22 is a linear or branched chain having 1 to 4 carbon atoms. It is preferred to burn the base. Examples of the calcined diyl group of the linear "branched chain" having a carbon number of 1i 4 include an anthracene group, an exoethyl group, a diindolyl group, a propane 2_diyl group, a tetradecylene group, and a dibutyl group. , 3_ two base. At the same time, for the bond of the benzene ring of Z and Z2, it is preferably 丨, bond (paraposome) or 1,3-bond (meta), and 丨, 4_ bond (paraposome) Preferably. The polycarbonate diol (A) of the present invention has one hydroxyl group at each end of the molecular chain. Therefore, the polycarbonate diol (A) of the present invention is composed only of the repeating unit represented by the formula (1) and two hydroxyl groups at both ends of the molecular chain, and may be, for example, the following formula (3):

(In the formula, Z1 and Z2 are the same as defined above, and n represents an integer of the number of repeating units), and may be a repeating unit represented by the formula (1), and one or more other repeating units and molecules. A polycarbonate diol copolymer composed of two base groups on both ends of the bond. 324043 201242984 The ratio of the repeating unit represented by the above formula (1) to other repeating units is preferably 1:99 to 99:1, and preferably 30:70 to 99:1, and 50:50 to 99:1. Good, and 55:45 to 99:1 is especially good. The polycarbonate diol represented by the repeating unit represented by the above formula (1) and the two hydroxyl groups is particularly preferably a polycarbonate diol represented by the following formula (3a).

, OH (3a) (where η represents an integer of the number of repeating units). The repeating unit represented by the formula (1) of the polycarbonate diol (Α) of the present invention in terms of mechanical properties, financial hydrolysis property, heat resistance, and compatibility with various fields of applicability The number, content, and number average molecular weight are as follows. The number of repeating units represented by the formula (1) is preferably from 1 to 18, and preferably from 2 to 13. Meanwhile, the number average molecular weight of the polycarbonate diol (Α) of the present invention is preferably from 200 to 3,000, preferably from 300 to 2,000, more preferably from 400 to 1,000. If the number average molecular weight is too high, the melting point will become high and it will be difficult to use. Meanwhile, when the number average molecular weight is too low, the number of carbonate bonds is reduced, and it is difficult to exhibit the properties as a polycarbonate diol. The polycarbonate diol of the present invention can be produced by a known method such as a carbonate method or a phosgene method, by using an aromatic diol compound, a carbonate or phosgene, etc., 324043 10 8 201242984. Among them, it is preferably a carbonate method. As the carbonate method, for example, the following Process 8 is preferred. The method A is as shown in the following reaction formula, and the aromatic dimerization is carried out. The carbon diol (3) is obtained by reacting the vinegar with the carbon in the presence of a touch. Methods. [Method A] Ζ1"0^Ζ2. Η +, again. 』2 ___ (4) (5) , person, winter η (3) ° In the above formula related to the method, R1 and R2 represent a carbon group of 1 ^ 6 which may have a substituent, or Indicates a dialkyl group having a carbon number of 2 to 4. η indicates the number of repeating units, which is preferably from i to 18, and preferably from 2 to ΐ3. In the above-mentioned Process A, in the case of the vinegar exchange reaction, since the alcohol (_, coffee, etc.) derived from the carbonated product (5) is by-produced, it is preferred to carry out the reaction while removing it by distillation or the like. At the same time, in the above-mentioned Process A, if carbonic acid is used as the carbonic acid S (5), the glycol which is by-produced from the carbonated vinegar is deliberately removed by steaming or the like. The reaction is carried out. At the same time, the [Formula B] towel of (4) is detailed in the case of the compound (4), the carbonate (5) and the transesterification reaction. The polycarbonate diol (A) according to the present invention is a polycarbonate composed of 324043 11 201242984 repeating unit represented by the formula (1), one or more other repeating units and two hydroxyl groups at both ends of the molecular chain. In the case of the diol copolymer, the other repeating unit' is not particularly limited as long as it has a carbonate structure, but the melting point or glass transition temperature of the obtained polyurethane compound can be lowered, and it is preferably the following formula. (2) Representation of the repeating unit. (2) In the formula, Z3 represents a linear or branched chain of a dialkyl group having 2 to 10 carbon atoms which may have a substituent, a ring-burning diyl group having a carbon number of 3 to 1 Å which may have a substituent or Any one having an alkyl 2 group having an alicyclic structure and having a carbon number of 5 to 1 Å in the main chain having a substituent. Here, the "substituent" may be any group which is not related to the subsequent amine esterification reaction. The alkyl group of a linear or branched chain having a carbon number of 2 to 1 Å represented by Z3 may, for example, be an exoethyl group, a triadenylene group, a propane-1,2-diyl group, a tetradecylene group or a butane-1. , a 3-diyl group, a penta-indenyl group, a hexamethylene group, a hepethylene group, an octadecyl group, a decamethylene group, etc. As the cycloalkyldiyl group having 3 to 10 carbon atoms represented by the above Z3, Out = propane-1' 2~diyl, cyclobutane-1,3-diyl, cyclopentane-1,2-diyl, ^hexane-1,2-diyl, cyclohexane_13_ Diyl, cyclohexane_14_diyl, =heptane-1' 4-diyl, cyclooctyl n 5 diyl, cycloazepane-i 5_diyl, % hexadecane: 1' 6~ diyl , adamantane-1,3-diyl, etc. As an alkyl-based group having an alicyclic structure and having an alicyclic structure of 5 to 1 Å in the main chain of the formula Z3, a cyclopropane- 1,2-di-indenylene, cyclobutane-1,3-two 324043 8 12 201242984 methylene, cyclopentane-1,2-dimethylene, cyclopenta-1,3_dimethylene Base, cyclohexane-1,2-di-indenylene, cyclohexane-di-indenyl, cyclohexane-1-tetramethyl, cyclohexane-1,2-diethyl, ring Hexane-l3-diethyl, cyclohexane-1,4-diethyl, cycloheptane-i,4-di-indenylene, cyclooctane-1,5-di-indenyl, etc. In the above, the Z3 is preferably a linear alkanediyl group having 3 to 6 carbon atoms or an alkanediyl group having 6 to 8 carbon atoms having an alicyclic structure in the main chain. The z3, in particular, is selected from the group consisting of Sanya. Methyl, butane-indole, "diyl, pentane-15-diyl, hexane-hydrazine, 6-diyl, cyclohexane-1,3-dimethylene, cyclohexane-L 4_ One or more of the group formed by the dimethylene group is preferable. That is, the polycarbonate diol (A) according to the present invention is a repeating unit represented by the formula (1), and a repeating unit represented by the formula (2) The two hydroxyl groups at both ends of the molecular chain may be, for example, a random copolymerized polycarbonate diol copolymer represented by the following formula (3).

(wherein Z, Z2 and z3 are the same as defined above, and n represents an integer of the number of repeating units). The molar ratio of the polycarbonate to the alcohol copolymer [[the repeating unit V represented by the formula (1) (the repeating unit represented by the formula (2))] is preferably 1/9 to 9/1, and is 1/5 to 5 /1 is better' and more preferably 1/3 to 3/1. In terms of mechanical properties, hydrolysis resistance, heat resistance, weather resistance, and in terms of suitability in various fields, polycarbonate The number, content, number average molecular weight, and the like of the repeating unit represented by the formula (1) 324043 13 201242984 and (2) of the alcohol copolymer are as follows. The repeating unit represented by the formula (1) and the repeating unit represented by the formula (2) can be embedded. The segment copolymerization ' can also be randomly copolymerized. The number of repeating units represented by the formula (1) is preferably from 1 to 20, and preferably from 2 to 15 in the polycarbonate diol copolymer, the repeating unit The content is preferably from 10 to 90 mol%, and preferably from 25 to 75 mol%. The number of repeating units represented by the formula (2) is preferably from 1 to 30, and preferably from 2 to 20 in the polycarbonate. In the diol copolymer, the content of the repeating unit is preferably from 10 to 90 mol%, and preferably from 25 to 75 mol%. The number average molecular weight of the polycarbonate diol copolymer of the present invention is preferably It is preferably from 200 to 3, 〇〇〇, and preferably from 300 to 2,000, more preferably from 900 to 1,500. Other desirable physical properties of the polycarbonate diol (A) according to the present invention are as follows The Hazen unit color number (APHA) specified in JIS K 1557 is preferably 200 or less, preferably 1 or less, more preferably 70 or less, and preferably 1 to 60. It is preferably from 35 to 600 mgKOH/g, and preferably from 50 to 400 mg KOH/g, preferably from 100 to 150 mgKOH/g, more preferably from no to i3 〇mg KOH/g. The acid value is preferably less than 1 mgKOH/g, and Preferably, it is 01 mgKOH/g or less, and more preferably 0.01 to 0.05 mg KOH/g. The melting point is preferably -100 to +250 ° C, and is -go to +200. (: preferably, 324043 14 201242984 -20 to +170 ° C is more preferred, and preferably 0 to 160 ° C. The glass transition temperature is preferably -80 to +50 ° C, and is preferably -60 to +20 ° C, and -55 More preferably -20 ° C. Viscosity is preferably 10 to 10 000 cp (75 ° C), and preferably 50 to 5,000 cp (75 ° C), and 100 to 1,500 cp (75 ° C) More preferably. As a method for producing the polycarbonate diol copolymer, known methods such as a carbonate method or a phosgene method are used. The method of reacting an aromatic diol compound with an aliphatic dihydroxy compound, a carbonate, phosgene, etc., etc. Among these methods, a carbonate method is preferable. As a carbonate method, the following is mentioned, for example. Method B is preferred. Process B is a transesterification of an aromatic dihydroxy compound (4), a carbonate (5) and an aliphatic dihydroxy compound (6) in the presence or absence of a catalyst as shown in the following reaction formula After the reaction, a method of obtaining a polycarbonate diol copolymer (3') is obtained. In the reaction formula of the following Process B, the reaction formula is simply described. Therefore, as the polycarbonate diol copolymer (3'), only the constituent unit derived from the aliphatic dihydroxy compound (6) is present on the left end. . However, the terminal is not limited to a constituent unit derived from the aliphatic dihydroxy compound (6). 324043 15 201242984 [Method B] HO〆

OH (4) Z2

(5)

HO—Z3-〇H (6)

In the above formula relating to Process B, r1, r2, z3 and the same n are the same as the above-mentioned phase B, and in the case of the exchange reaction of S, the alcohol (10)H, _, etc. derived from the carbonated vinegar (5) is by-produced. Therefore, it is preferable to carry out the reaction while removing it by _ or the like. At the same time, in the above-mentioned Process B, if carbonic acid (such as carbonic acid) is used, the carbonic acid (4) carbon is used for the purpose of removing the diol from the carbonated vinegar, and it is removed by steaming. reaction. The aromatic di-based compound used in the polycarbonate of the present invention is represented by the following formula (4). H〇/ Χ〇Η (4) In the formula, Ζ1 and Ζ2 are the same as described above, and each independently represents a linear or branched alkyl alkanediyl group having a carbon number of 10/10. Specific examples of the alkanediyl group are, for example, the above-mentioned, and are preferably a secondary or branched bond group having a carbon number of 1 to 4. At the same time, it is preferably a 1,4-bond (paraposome) or a 3-3-bond (intermediate) and is a 1,4-bond (parent). 324043 201242984 As an especially desirable aromatic woven compound (4), it can be mentioned! 4_ phenylenediethanol, 1,4-diphenylethanol, phenyldipropanol, 14-benzene dibutanol, 1,3-didimethylethanol, u-phenylenediethanol, 13-stall dipropanol, u-benzene Butanol K4,ylmethylphenyl)taucanol, 3-[4|transethylidene)phenyl] propylidene is a compound having a linear or branched chain of a carbonic number of 1 to 4. The carbon (4) (5)' which can be used in the polycarbonate diol according to the present invention is not limited, but it is desirable to select an alcohol which is produced by carbonic acid vinegar by a suitable selection. For example, di(tetra)carbonate, diaryl carbonate, alkylene carbonate, and the like can be given. As the carbonated vinegar, it is preferable to have a hospital base having a carbon number of 1 to 6, and it is preferably a carbonic acid di(tetra) having a carbon number of 1 to 4, and specific examples thereof include dinonyl carbonate and diethyl carbonate. Examples of the diaryl carbonate include diphenyl carbonate and the like. The alkylene carbonate is preferably an alkylene carbonate having a carbon number of 2 to 4, and the alkylene carbonate is specifically exemplified by ethyl acetate, propyl carbonate, and carbonic acid. Such a carbon-ray towel is preferably a dialkyl carbonate having an alkyl group having a carbon number of 4 to 4 in terms of ease of removal of a by-produced alcohol, and is preferably a dinonyl carbonate. The aliphatic di-based compound which can be used in the polycarbonate diol according to the present invention is represented by the following formula (6). HO—Z3-〇H (6) wherein 'Ζ3 is the same as defined above, and represents a linear or branched alkyl alkanediyl group having 2 to 10 carbon atoms which may have a substituent, and a carbon number of 3 to 10 which may have a substituent The cycloalkanediyl' or the carbon having an alicyclic structure in the main chain which may have a substituent 324043 17 201242984 Any one of the 5 to 10 calcined bases. Z3 is an alkanediyl group having 2 to 1 carbon atoms, and examples of the alkanediol include ethyl alcohol, 1,3-propanediol, L4-butanediol, U5_pentanediol, and 1,^. Alkyl alcohol, 1, heptane diol, 1,8-octyl diol, 1,9-hydrazine diol, 1,10-decane diol, and the like. The carbon chain which is a part of the alkanediyl moiety is branched, and examples thereof include 13-butanediol, 3-methylpentane-i, 5-diol, 2-ethylhexane_1> Glycol, neopentyl glycol, 2-methyl-1,8-octanediol, and the like. Z 疋% 3 to 1 〇 烧 烧 , , , , , , , , , , , , , , , , , , , , 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为Glycol, cyclohexane-1,2-diol, cyclohexane-1,3-diol, cyclohexane-oxime, 4-diol, J-heptane-1,4-diol, cyclooctane Alkane-1,5-diol, cyclodecane-丨, 5-diol, cyclodecane-1,6-diol, adamantane-1,3-diol, etc. have an alicyclic structure in the main chain The carbon number is 5 to the ring of the second base. As the %: burned alcohol, it can be exemplified by cyclopropanone _ 丨, 2_ dimethanol, cyclobutane 1, d~ dinonol, cyclopentane-1, 3. - Didecyl alcohol, 1,4-cyclohexanedetyl alcohol, and the like. Among the above, in terms of usability and easy availability, it is preferably a cesium, a butane diol, a 1,5-pentane diol, a hexamethylene diol or the like having a carbon number of 4 to 8 The alcohol is preferably an aliphatic diol having an alicyclic structure having a carbon number of 5 to 8 such as a diol having 4 to 6 carbon atoms or 1,4-cyclohexyl dimethanol. The catalyst used in the production of the polycarbonate diol according to the present invention may be a catalyst (transesterification catalyst) used in a usual transesterification reaction. For example, an alkali metal compound, an alkaline earth metal compound, an aluminum compound, a zinc compound, a manganese compound, a nickel compound, a ruthenium compound, 鍅 324043 201242984 * compound, a titanium compound, and an organotin compound are preferable. As the alkali metal compound, an alkali metal hydroxide (hydrogen oxygen) can be mentioned.  Lithium carbonate, sodium hydroxide, potassium hydroxide, etc.), alkali metal carbonate (lithium carbonate, sodium carbonate, potassium carbonate, etc.), alkali metal carboxylate (lithium acetate, sodium acetate, potassium acetate, etc.), alkali metal An alkoxide (a lithium lanthanum oxide, a sodium methoxide, a potassium third butyl oxide, etc.), etc., and an alkaline earth metal compound, a hydroxide of an alkaline earth metal (magnesium hydroxide, etc.), an alkaline earth type A metal alkoxide (magnesium oxide, etc.) or the like. The above-mentioned compound may, for example, be an alumina compound such as an intumescent oxide (Ming ethoxylate, aluminum isopropoxide, or aluminum second butoxide) or an aluminum acetonate or the like. Examples of the zinc compound include a zinc carboxylate (such as acetic acid) and acetonitrile zinc. Examples of the manganese compound include a manganese carboxylate (manganese acetate or the like), acetonitrile, and the like. Examples of the nickel compound include a carboxylate of nickel (such as nickel acetate), nickel acetonitrile, and the like. Examples of the ruthenium compound include a ruthenium carboxylate (such as ruthenium acetate) and a decane oxide. Examples of the zirconium compound include zirconium alkoxide (zirconium oxide, ruthenium oxide, etc.) and B. Zirconium acetonide and the like. Examples of the titanium compound include titanium sintered oxide (titanium tetraethoxy oxide, titanium tetrapropoxide, titanium tetrabutoxide, tetracyclohexyl titanate, tetraphenylmethyl titanate, etc.), and titanium. Telluride (tributyltitanium stearate, isopropoxytitanyl stearate, etc.), titanium chelate (bis(acetonitrile)diisopropoxytitanium, dihydroxy•dilactic acid titanium, etc. )Wait. Examples of the organotin compound include dibutyltin oxide, 324043 19 201242984 butyltin diacetate, dibutyltin dilaurate, and the like. Further, the carboxylic acid in the respective carboxylate salts is preferably a slow acid acid having a carbon number of 2 to 30 and preferably a carboxylic acid having a carbon number of 2 to 18. Each alkoxide is preferably an alkoxy group having 1 to 30 carbon atoms, and preferably an alkoxy group having 2 to 18 carbon atoms. Among the above-mentioned catalysts, it is preferable to use a titanium compound or an organotin compound, and it is preferable to use a compound, and a titanium alkoxide is more preferable. Among the titanium alkoxides, niobium tetrakis oxide, tetrakiladene oxide, and titanium tetrabutoxide are preferred, and titanium tetrabutoxide is particularly preferred. Meanwhile, the above-mentioned aromatic di-based compound (4), carbonate (5), aliphatic dihydroxy compound (6) and catalyst may be used singly or in combination of two or more kinds. The transesterification reaction in the method for producing a polycarbonate diol according to the present invention may be carried out in the presence or absence of a catalyst, but in terms of reaction efficiency, it is preferably carried out in the presence of a catalyst. The reaction temperature and the reaction pressure in the hydrazine exchange reaction vary depending on the type of the acid vinegar (5) and the base compound (8), but it is preferable to use an aromatic di-based group such as 1'4 to stupid methanol in the case of the t method A. The compound (4) is substantially inconsistent with the conditions of the method B, and the conditions of the aromatic second compound (4) and the aliphatic-based compound (8) are substantially ignored. The reaction temperature is preferably from 90 to 230 C'. The reaction pressure is preferably from atmospheric pressure to 3 Torr to 5 Torr. At the same time, although the reaction can be carried out in air, carbon dioxide or an inert gas (nitrogen, A, hydrazine, etc.) = ambient or in a gas stream, it is preferred to carry out the reaction under the atmosphere of an inert gas or in a gas stream. Further, in terms of reactivity, in terms of reactivity, in the case of Process A, 324043 8 20 201242984 is added to the total amount of the aromatic dihydroxy compound (4) and the carbonate (5) at the start of the reaction. In the case of B, the total amount of the aromatic di-based compound (4), the carbonated vinegar (5), and the aliphatic dihydroxy compound (6) at the start of the reaction is preferably based on the weight of the catalyst. i to 2 〇, 〇〇〇 ppm, and preferably 10 to 5, OOO ppm, and more preferably 1 to 4, 〇〇〇 ppm. At the same time, an aromatic di-based compound (4) such as a ruthenium or a 4-diphenyl sterol obtained by reacting an aliphatic dihydroxy compound (6) with a carbonate (5) The polyglycol diol copolymer is obtained after the brewing exchange reaction is carried out in the presence or absence of a catalyst. And a high molecular weight poly (tetra) diol obtained by reacting an aromatic di-based compound (4) such as 1'4-benzene dimethanol with carbonic acid vinegar (5), and an aliphatic di-based compound (8)' in the presence of After the exchange reaction is carried out, a polycarbonate copolymer is obtained. The average molecular weight of the polycarbonate diol (Α) according to the present invention is prepared by changing the reaction molar ratio of the aromatic di-based compound (4), the carbonic acid g|(5), and the aliphatic compound (6). ^ At the same time, if the average molecular weight of the produced polycarbonate or polycarboxylate diol is less than the target average molecular weight, and then under reduced pressure; = group di-based compound (4) and / or aliphatic di-based compound ( 6) Considering: If the average molecular weight is greater than the target average molecular weight, add the aromatic trans-substrate (4) and/or the aliphatic di-based compound (6) and then carry out: ^ reaction to obtain the target average molecular weight of the poly Determining = carbonate diol copolymer. Alcohol or poly 324043 at the same time as the poly-carbonated §|diol copolymer of the present invention, the repeating unit 21 201242984 i and the molar ratio, depending on the aromatic di-based compound (4) and the aliphatic di-based compound (6) The ear is modulated by a change or the like. (Polyisocyanate compound (B)) The polyisocyanate g which can be used in the present invention is a compound (8), and is particularly limited. (4) The u-phenylene diisocyanate is used, and 1 > Phenyl diisocyanate s, 2,4-benzylidene diisocyanate from (10) m monobenzylidene: isocyanate, 4,4, _ diphenylene acetonate diiso-acid vinegar (MDI 2, 4-i-extension of methacrylic acid diisocyanate, 4'-diisocyanatobiphenyl, 3,3-dimethyl-4,4,-diisocyanatobiphenyl, 3 3,_ Dimethyl-4,4-diisocyanatodiphenylmethane, anthracene, 5_thylene naphthalene diisocyanate S曰4'4, 4-diylcarbazone triisocyanate An aromatic polyisocyanate compound such as isocyanato-p-hydroxyl-isocyanate or p-isocyanatophenylsulfonyl isocyanate; ethyl diisocyanate, tetramethylene diisocyanate, diiso) Hexamethylene cyanate (HDI), methylene methylene diisocyanate, 1,6, U-undecane triisocyanate, 2,24-trimethylhexamethylene diisocyanate, Iridic acid diisocyanate, methyl 2,6-diisocyanatohexanoate, bis(2-isocyanatoethyl) An aliphatic polyisocyanate compound such as butylene diacetate, bis(2-diisocyanatoethyl)carbonate or 2-isocyanatoethyl 2,6-diisocyanatohexanoate; isophorone Diisocyanate (IPDI), 4, 4,-dicyclohexylmethane diisocyanate (hydrogenated MDI), cyclohexyl diisocyanate, methylcyclohexyl diisocyanate (hydrogenated TDI), double (2 -isocyanatoethyl)- 4 -cyclohexene-1,2-dicarboxylate, 2, 5-norbornane diisocyanate, 2,6-norbornane diisocyanate, etc. alicyclic polyisocyanate compound Wait. These polyisocyanate compounds may be used singly or in combination of several kinds. 324043 22 8 201242984 The isocyanate group per molecule of the above polyisocyanate compound, although usually two, does not gel the polyurethane compound of the present invention.  In the range, polyisocyanuric acid having three or more isophthalic acid groups such as triphenylmethane triisocyanate can be used. Among the above polyisocyanate compounds, s is 4,4'-diphenylene diisocyanate (MDI), isophorone diisocyanate (IPDI), 4, 4 in terms of control of reactivity and imparting strength. ,-Dicyclohexylmethane diisocyanate (hydrogenated MDI) is preferred. ((meth) acrylate compound (〇) having a hydroxyl group as a (mercapto) acrylate compound having one or more hydroxyl groups in the molecule which can be used in the present invention (hereinafter also referred to as "(meth) acrylate compound (hereinafter also referred to as "(meth) acrylate compound ( C)") is not particularly limited, and specific examples thereof include ethylene glycol mono(meth)acrylate, propylene glycol mono(meth)acrylate, butanediol mono(meth)acrylate, and pentane. Glycol mono(meth)acrylate, hexanediol mono(meth)acrylate, diethylene glycol mono(meth)acrylate, dipropylene glycol mono(indenyl)glycolate,diethylene Alcohol mono(mercapto) acrylate, tripropylene glycol mono(decyl) acrylate, tetraethylene glycol mono(mercapto) acrylate, polyethylene glycol mono(meth) acrylate, polypropylene glycol single (a) Bis) acrylate, neopentyl glycol mono(indenyl) acrylate, ethoxylated neopentyl glycol mono(indenyl) acrylate, hydroxytrimercaptoacetic acid neopentyl alcohol mono(meth) acrylate, etc. Alcohol mono(indenyl) acrylate vinegar; trimethyl methacrylate Acetate, acetoacetate, ethoxylated trisyl propyl propyl acetonide (methyl) acrylic acid @ 、, propane trioxide, mercaptopropene, mono(methyl) acrylate, tris(2-yl) Ethyl)trimeric isocyanuric acid mono(indenyl) acrylate, glycerol mono(indenyl) acrylate vinegar, trimethyl methacrylic acid bis(indenyl) propylene 324043 23 201242984 vinegar, ethoxylated Tri-methylpropane di(meth)acrylate vinegar, propoxylated trimethylolpropane di(meth)acrylate, tris(2-hydroxyethyl)trimeric isocyanate di(meth)acrylate, glycerol II Mono-(meth) acrylates and di(meth) acrylates of triols such as acrylates, or a part or groups of hydroxyl groups of such alcohols modified by alkyl or ε-caprolactone (meth) acrylate, pentaerythritol mono (indenyl) acrylate, dipentaerythritol mono (meth) acrylate, ditrimethylolpropane mono (meth) acrylate, neopentyl alcohol Di(meth)acrylate, dipentaerythritol di(meth)acrylate, ditrihydroxymethylpropane di(methyl)propionate, neopentyl Four (meth) acrylate, dipentaerythritol tris(decyl) acrylate, ditrimethylolpropane tri(meth) acrylate, dipentaerythritol tetrakis(meth) acrylate, etc. a polyfunctional (meth) acrylate having a hydroxyl group or more, or a compound having a hydroxyl group, or a polyfunctional (meth) acrylate having a hydroxyl group modified by a part of hydroxyl groups of the alcohols via an alkyl group or ε-caprolactone These (meth) acrylate compounds (c) may be used singly or in combination of several kinds. Among the above (fluorenyl) acrylate compounds (C), low viscosity and low cost are required. Generally, it is preferably a mono(meth)acrylate of a glycol such as ethylene glycol mono(indenyl)acrylate, propylene glycol mono(meth)acrylate, butanediol mono(indenyl)acrylate, and Ethylene glycol mono(meth)acrylate is preferred. The polyurethane compound of the present invention can be composed of a polycarbonate diol, a polyisocyanate compound and a (fluorenyl) acrylic acid having one or more hydroxyl groups in the molecule. The ester compound (C) is obtained by a reaction. The details of the reaction can be carried out in accordance with the well-known method for producing a polyurethane compound, although it will be described later. Meanwhile, for example, after the polycarbonate diol (Α) is reacted with the polyisocyanate compound 324043 24 201242984% (B) to obtain a polyurethane prepolymer having an isocyanate group at the end, the aforementioned polyurethane prepolymer and the molecule are obtained. (Methyl) C with one or more hydroxyl groups in it.  The enoate compound (C) is reacted to produce the polyurethane compound of the present invention. (Polymer group containing an acidic group))) In addition to the carbonate diol (A), the polyisocyanate compound (B), and the (meth) acrylate compound (C) having one or more groups in the molecule, The polyurethane compound of the invention may be a compound obtained by reacting a polyol (D) having an acidic group. The acid group-containing polyol (D) is not particularly limited as long as it is a compound containing two or more hydroxyl groups and one or more acidic groups in one molecule. Examples of the acidic group include a carboxyl group, a continuation base, an acid-filling group, and an inert group. Among the above-mentioned acidic group-containing polyols (D), a compound having two or more hydroxyl groups and one or more carboxyl groups in one molecule is preferable, and a compound having two hydroxyl groups and one carboxyl group in one molecule is preferable. Specific examples of the acidic group-containing polyol (D) include dimethylol alkanoic acid such as 2,2-dimethylolpropionic acid and 2,2-dihydroxydecylbutyric acid, and N, N. - bishydroxyethylglycine, N,N-bishydroxyethylalanine, 3,4-dihydroxybutanesulfonic acid, 3,6-dihydroxy-2-indolylbenzenesulfonic acid, acid-containing poly Ether polyester, polyester polyol containing an acidic group, and the like. Among them, it is preferable to obtain a di-methyl succinic acid. In this case, the number of carbon atoms of the acid-burning acid is preferably 4 or less, and more preferably 2,2-dihydroxymercaptopropionic acid. The acidic group-containing polyol (D) may be used alone or in combination of two or more. 324043 25 201242984 Meanwhile, the polyurethane compound of the present invention may be composed of a polycarbonate diol (A), a polyisocyanate compound (B), a (meth) acrylate compound (C) having one or more hydroxyl groups in the molecule, and an acidic group. The polyol (D) is obtained by reaction. The details of the reaction can be carried out in accordance with a known method for producing a polyurethane compound, as will be described later. Meanwhile, for example, after the polycarbonate diol (A), the polyisocyanate compound (B) and the acid group-containing polyol (D) are reacted to obtain a polyurethane prepolymer having an isocyanate group at the end, the aforementioned polyurethane is allowed to be obtained. The prepolymer is reacted with a (mercapto) acrylate compound (C) having one or more hydroxyl groups in the molecule to produce a polyurethane compound of the present invention. (Chain Extender (E)) The polyurethane compound of the present invention may be a polycarbonate diol (A), a polyisocyanate compound (B), or a (fluorenyl) acrylate compound having one or more hydroxyl groups in the molecule ( C) A compound obtained by reacting an acidic group-containing polyol (D) having an optional component with a chain extender (E). The chain extender (E) may, for example, be a compound reactive with an isocyanate group. For example, ethylenediamine, 1,4-butanediamine, 2-methyl-1,5-pentanediamine, 1,4-butanediamine, 1,6-exexylenediamine, 1,4-stretch Hexamethylenediamine, 3-aminomethyl-3,5,5-trimethylcyclohexylamine, 1,3-bis(aminomercapto)cyclohexane, xylylenediamine, piperidine, hexamethylenediamine Amine compounds such as hydrazine, hydrazine, 2, 5-dimethylpiperidin, diethylenetriamine, and triethylenetetramine, ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexane A diol compound such as a diol, a polyalkylene glycol represented by polyethylene glycol, water or the like, and preferably a primary diamine compound. These compounds may be used singly or in combination of two or more kinds. 324043 26 8 201242984 % The method of adding the chain extender (E) may be a one shot method in which one reaction is carried out once with each raw material, or may be carried out at the molecular end.  A prepolymer process for the reaction of a polyurethane prepolymer having an isocyanate group. The polyurethane prepolymer 9 can be obtained by reacting a polycarbonate diol (A), a polyisocyanate compound (B), and an acid group-containing polyol (D) having an optional component. Meanwhile, the polyurethane prepolymer may be composed of a polycarbonate diol (A), a polyisocyanate compound (B), an acid group-containing polyol (D) having an optional component, and one or more hydroxyl groups in the molecule ( The thiol) acrylate compound (C) is obtained by a reaction. In this case, when the (meth) acrylate compound (C) having one or more kinds of radicals in the molecule has only one hydroxyl group in the molecule, the thiol group having one or more hydroxyl groups in the molecule is added in a large amount. In the case of the acrylate compound (C), the isocyanate group of the polyurethane prepolymer is sealed by the (indenyl) acrylate compound (C) having one or more hydroxyl groups in the molecule, and the chain extender cannot be used. E) The situation of the reaction. The amount of the aforementioned chain extender (E) can be appropriately selected. When the aqueous polyurethane dispersion is produced by the prepolymer method, the number of moles of the group reactive with isocyanate in the chain extender other than water may be the isocyanate group in the polyurethane prepolymer. A chain extender is added in a manner that is less than 2 times the number of ears. The molar ratio of the polyurethane prepolymer to the chain extender is preferably from 1:1 to 〇.  8 : 1 mixed. The polyurethane compound of the present invention can be produced by reacting a polycarbonate diol (A) or a polyisocyanate compound (B) with a (fluorenyl) acrylate compound (C) having at least one hydroxyl group. The reaction temperature is 0 to 150 ° C, and is preferably 324043 27 201242984 20 to 100 ° C. At the same time, the reaction can be carried out under the atmosphere of an inert gas, in the ambient environment of the air, or in a mixed environment of inert gas and air. When using air, dry air should be used. The ratio of the above three components is preferably the total number of moles of the polycarbonate diol (A) and the hydroxyl group contained in the hydroxyl group-containing (fluorenyl) acrylate compound (C), and the polyisocyanate compound (B). The ratio of the number of moles of the isocyanato group contained (0H/NC0) becomes a ratio of 100/100 to 110/100. By making the total number of moles of hydroxyl groups more than the number of moles of isocyanate groups, residual unreacted isocyanate groups can be reduced. The catalyst which can be used in the above reaction is a catalyst (amine esterification catalyst) used in a usual amine esterification reaction. Although not particularly limited, specific examples thereof include organotin compounds such as dibutyltin diacetate and dibutyltin dilaurate; titanium tetraacetate, titanium diisopropyloxybis(ethylacetamidine acetate), and the like. An organic titanium compound; an organic ruthenium compound such as zirconium tetraacetate or zirconium dibutoxide bis(ethyl acetonitrile acetate); a tertiary amine compound such as triethylamine. These amine esterification catalysts may be used singly or in combination of several kinds. Among these catalysts, although an organotin compound or an organic zirconium compound is preferable, among them, dibutyltin dilaurate and tetraethylguanidinium zirconate are more preferable. The amount of the amine esterification catalyst to be added is preferably 0. The amount of the amine esterification catalyst is preferably 0.  00005% by weight to 0.  01% by weight, and 0. 0001% by weight to 0. 005% by weight is preferred, and is 0. 0003% by weight to 0.  003% by weight is especially preferred. In the above reaction, a polymerization inhibitor or an antioxidant may be used to inhibit the polymerization of the (fluorenyl) acrylate group in the reaction at 324043 28 8 201242984. Although not particularly limited, specific examples thereof include hydroquinone, p-nonyloxyphenol, 2,4-dimercapto-6-t-butylphenol, p-alum, 2,5-dihydroxy- P-benzoquinone and the like. These polymerization inhibitors or antioxidants may be used singly or in combination of several kinds. The amount of the polymerization inhibitor or the antioxidant is preferably 0. The amount of the polymerization inhibitor or the antioxidant is preferably added to the total weight of the polycarbonate diol (A), the polyisocyanate compound (B) and the (meth) acrylate compound having a hydroxyl group. 00005% by weight to 0. 01% by weight ’ and 0. 0001% by weight to 0. 005% by weight is preferred, and 0. 0003% by weight to 〇.  〇〇 3 wt% is especially good. Further, the above reaction can be carried out by using an organic solvent which does not have an active hydrogen group reactive with an isocyanate group, and the resulting reaction solution is directly used as the polyurethane solution of the present invention. The organic solvent is not particularly limited, and specific examples thereof include a ketone solvent such as acetone, mercaptoethyl ketone, decyl isobutyl ketone or cyclohexanone, or ethyl acetate, butyl acetate, propylene glycol monoterpene ether acetate. An ester solvent such as ester, propylene glycol monoethyl ether acetate or dipropylene glycol monoterpene ether acetate, or ethylene glycol dioxime ether, ethylene glycol diethyl ether, dipropylene glycol dimethyl ether, propanol monoethyl ether, diethylene glycol The ethers such as the two mysteries and the triethylene glycol diacetate are benzene, benzene, diphenyl, tetracyl alcohol, and the like. These organic solvents may be used singly or in combination of several kinds. The amount of the organic solvent to be used is preferably such that the total weight of the polycarbonate diol (the polyisocyanate compound (B) and the (meth) acrylate compound (c) to be used and the weight ratio of the organic solvent is 1/. The ratio of 9 to 9/1 is preferably 2/8 to 8/2, and is preferably 3/7 to 7/3 324043 29 201242984. At the same time, it can be used to separate the polyurethane compound. Dissolving or dispersing in an organic solvent to form a liquid or paste-like polyurethane solution. At this time, the solid concentration of the polyurethane compound is preferably from 3 to 95% by weight. The liquid or paste-like polyurethane/gluten solution can be utilized as a The organic solvent to be used is not particularly limited, and is the same organic solvent as the above-mentioned reaction in the above-mentioned reaction. (Polyurethane composition) The polyurethane composition of the present invention (hardening) The resin composition) is characterized by containing the polyamine ester compound of the present invention, a polymerization initiator (G), and optionally a compound (F) having a polymerizable unsaturated bond other than the polyurethane compound of the present invention. The polymerization initiator (G) used in the ester composition may, for example, be a photopolymerization initiator which is usually used. The photopolymerization initiator is not particularly limited, and examples thereof include acetophenone and 2, 2-diethoxy acetophenone, p-dimethylamino acetophenone, benzophenone, 2-aluminum diphenyl f, p, p, bis bis diethylamino benzophenone, Benzoin ether, benzoin n-propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin n-butyl ether, benzoin dimethyl ketal, thioxanthone, p-isopropyl-α-hydroxyisobutyl benzophenone, 2 , 2_dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1[4-(indolylthio)phenyl]-2-(anthracene-morpholine Propyl-1-one, 2-hydroxy-2-indoleyl-indole-phenylpropanone, 2,4,6-dimercaptobenzophenone, 4-methyldiphenylfluorene g, double (2, 4, 6-dimethylbenzimidyl)-phenylphosphine oxide, 2,2-dimethoxyoxy 324043 8 30 201242984 Qin-1,2-diphenylethanone, etc. Ideally Examples include hydroxycyclohexyl phenyl ketone, bis(2,4,6-trimethylbenzylidene) phenylphosphine oxide, etc. 1 et al.  I may be used alone or in combination of several initiators. The amount of the photopolymerization initiator to be added is preferably 0% by weight based on the weight of the polyurethane compound. It is preferably from 3% by weight to 5% by weight, and preferably from 5% by weight to 5% by weight. The compound (F) having a polymerizable unsaturated bond used in the polyurethane composition of the present invention is not particularly limited, and specific examples thereof include, for example, (meth)acrylic acid vinegar and (meth)acrylic acid Vinegar, isopropyl (meth)acrylate, n-butyl (meth)acrylate, tert-butyl (meth)acrylate, (meth)acrylic acid, isobutyl vinegar, etc. (meth)acrylic acid vinegar , (Methyl)acrylic acid 2_ylidylethyl vinegar, (methyl)propionic acid 2-propyl propyl vinegar, (methyl) acrylic acid 3 dimethyl propyl vinegar, (曱a single acetate of (meth)acrylic acid such as butyl acetoacetate and a diol of 2 to 8 carbon atoms, or butyl diol bis(meth) acrylate vinegar or hexane diol Di(meth)acrylate, ethoxylated hexanediol-(mercapto)acrylic acid vinegar, propane oxide hexane di(meth)acrylate, diethylene glycol bis(indenyl)acrylate, Polyethylene glycol di(meth) acrylate, polypropylene glycol di(meth) acrylate, neopentyl glycol bis(indenyl) acrylate vine, ethoxylated neopentyl glycol bis(曱Di(meth)acrylic acid vinegar, such as acrylic acid vinegar, or tris(methyl) acrylate vinegar, ethoxylated trimethyl propyl acetonate, propylene acrylate Trimethyl methacrylate tris(methyl) acrylate vinegar, tris(2-ylethyl)trimeric isocyanurate tris(meth) acrylate vinegar, tris(meth)acrylic acid Tris(methyl)propene vinegar, such as vinegar, or pentaerythritol bis(indenyl) acrylate, dipentaerythritol tris(meth) acrylate vinegar, 324043, 201242984 ditrihydroxy decyl propane Tris(fluorenyl) acrylate, neopentyltetrakis(mercapto) acrylate, dihydroxyl propyl propylene tetra(meth) acrylate, dipentaerythritol tetrakis(meth) acrylate, two new Pentaerythritol penta(indenyl) acrylate, ditrihydroxymercaptopropane pentoxide (decyl) acrylate, dipentaerythritol hexa(indenyl) acrylate, di-dithiopyranyl A polyfunctional (fluorenyl) group such as a methyl (meth) acrylate or a polyfunctional (fluorenyl) acrylate acid or a part of such (mercapto) acrylic acid vinegar substituted with an alkyl group or a 6-caprolactone Propylene A (mercapto) acrylate compound having 3 to 6 (fluorenyl) acrylonitrile groups in one molecule such as an acid ester. These polymerizable compounds may be used singly or in combination of several kinds. The amount of the compound (F) having a polymerizable unsaturated bond in 100 parts by weight of the polyamine vinegar compound is preferably 1 part by weight or less. Further, in the polyurethane composition of the present invention, a coloring pigment, an extender pigment, a bright pigment, a tackifier, a curing catalyst, an ultraviolet absorber, a light stabilizer, or a consumer may be used depending on the use or as needed. A general coating additive such as a foaming agent, a plasticizer, a surface conditioner, and a precipitating agent. These coating additives may be used singly or in combination of several kinds. Further, these additives are not particularly limited as long as they are well-known compounds, and can be used without impairing the properties of the polyurethane composition and the cured product thereof. ^ (Cured product) The cured product of the present invention is adjusted to an appropriate viscosity by an organic solvent or the like as needed, and is then subjected to energy rays such as ultraviolet rays, visible light, laser light, electron beam, X-ray, r-line, (four), microwave, and the like. It is irradiated on the above poly(tetra) composition, polymerized and hardened. Or it can be obtained by heat polymerization and hard 324043 32 201242984. The solvent used as the above organic solvent can be used without particular limitation. Specifically, for example, a ketone solvent such as acetone, mercaptoethyl ketone, decyl isobutyl ketone or cyclohexanone; or ethyl acetate or acetic acid; An ester solvent such as butyl ester, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate or dipropylene glycol monoterpene ether acetate; or ethylene glycol diterpene ether, ethylene glycol diethyl ether, dipropylene glycol dioxime ether, dipropylene glycol An ether solvent such as diethyl ether, triethylene glycol dimethylhydrazine or triethylene glycol diethyl ether; an aromatic solvent such as benzene, toluene, xylene or tetradecylbenzene. These organic solvents may be used singly or in combination of several kinds. The material to be coated or the material to be coated when the cured product of the present invention is obtained by coating or coating may be a resin such as metal, plastic, inorganic, wood, ABS resin or polycarbonate resin. (Aqueous polyurethane dispersion) The polyurethane resin of the present invention can be dispersed in an aqueous medium to form an aqueous polyurethane dispersion. Meanwhile, in obtaining the aqueous polyurethane dispersion of the present invention, the polycarbonate diol (A), the polyisocyanate compound (B), the (mercapto) acrylic acid S compound (C) and the aqueous medium are essential components, and The acid group-containing polyol (D) and the chain extender (E) are optional components. In the aqueous polyurethane dispersion of the present invention, a polyurethane compound obtained by reacting a polycarbonate diol (A) and a polyisocyanate compound (B) with a (meth) acrylate compound (C) is dispersed in a water system. Aqueous polyurethane dispersion in a medium; a polyurethane compound formed by reacting a polycarbonate diol (A), a polyisocyanate compound (B), a (fluorenyl) acrylate compound (C) with an acid group-containing polyol (D) , Aqueous polyamine 324043 dispersed in aqueous medium 33 201242984 = bulk poly-carbonic acid diol (A), polyisocyanate brewing compound (8), (comb compound (c) and bond extender (8) reaction formed by the money Acid i (a) dispersion in aqueous medium; polycarbon = human acetoacetate (8), (meth) acrylate vinegar / 曰 U matter 'dispersed in water-based media towel Dispersion: The polylin compound of the present invention is obtained by reacting a polyglycol diol (A), A, a compound (8), a (mercapto) propionate s compound (6), and an acid group-containing polyol (9). , at least to make polycarbonate diol (A), polyisocyanate After the reaction of the compound (8) and the compound (c) with the tribasic compound (D), the acid group is neutralized with a base, and the knife is dispersed in the aqueous medium towel to obtain an aqueous polyamine g. In the method for producing the aqueous polyurethane dispersion, the (meth) acrylate compound (C) may be reacted with the polyamine S prepolymer before dispersing the polyurethane prepolymer in an aqueous medium, or may be The aqueous system f is simultaneously reacted with the polyamine prepolymer, and may also be reacted with the polyurethane prepolymer after being dispersed in the aqueous medium. For example, the polyurethane compound of the present invention is composed of polycarbonate diol (A), polyisocyanate compound. When the (B), (fluorenyl) acrylate compound (c), the acid group-containing polyol (D) and the chain extender (E) are reacted, the polycarbonate diol (A) and the polyisocyanate compound can be obtained. (B) reacting with the acid group-containing polyol (D) to obtain a polyurethane prepolymer having an isocyanate group at the terminal, and neutralizing the acidic group derived from the aforementioned acid group-containing polyol to disperse it in the water system After the medium, react with the bond extender (E) And then reacting with a (mercapto) acrylate compound (c) having 324043 Λ 8 201242984 or more hydroxyl groups in the molecule. In the method for producing the aqueous polyurethane dispersion described above, (mercapto) acrylate compound (C) and The chain extender (E) may be reacted with the polyurethane prepolymer before dispersing the polyurethane prepolymer in the aqueous medium, or may be reacted with the aqueous medium simultaneously with the polyurethane prepolymer, or may be mixed with the polyurethane after being dispersed in the aqueous medium. Prepolymer reaction. As a base for neutralizing the aforementioned acidic group, tridecylamine, triethylamine, triisopropylamine, tributylamine, triethanolamine, N-decyldiethanolamine, An organic amine such as N-phenyldiethanolamine, dimethylethanolamine, diethylethanolamine, N-mercaptomorpholine or pyridine; an inorganic base such as sodium hydroxide or potassium hydroxide; or ammonia. Among them, organic amines are preferred, and tertiary amines are preferred, and triethylamine is preferred. These bases may be used singly or in combination of two or more. The aqueous medium may, for example, be water or a mixed medium of water and a hydrophilic organic solvent. The aqueous medium is preferably used in an amount of from 5 to 60% by weight based on the amount of the polyurethane resin in the aqueous polyurethane resin dispersion, and is preferably from 20 to 50% by weight. As the water, for example, tap water, ion-exchanged water, distilled water, ultrapure water, or the like may be mentioned. However, it is preferable to use ion-exchanged water in consideration of easiness of measurement or the disturbing timing of particles due to the influence of salt. Examples of the hydrophilic organic solvent include ketones such as propyl and ethyl decyl ketones, ethers such as esters, tetrahydrofuran and N-mercaptomorpholine, and dimethylformamide and N-mercaptotetrahydrogen. Anthraquinones such as pyrrolidone and N-ethyltetrahydropyrrolidone, and alcohols. These organic solvents may be used singly or in combination of two or more. 324043 35 201242984 (Aqueous polyurethane dispersion composition) The aqueous polyurethane dispersion of the present invention may be prepared by adding the above compound (F) having a polymerizable unsaturated bond and the above polymerization initiator (G) to prepare an aqueous polyurethane dispersion. Composition. Among the above-mentioned compositions, a general coating additive such as a pigment, a dye, a tackifier, a curing catalyst, an ultraviolet absorber, a light stabilizer, an antifoaming agent, a plasticizer, a surface conditioner, and a prepreventing agent may be contained as needed. 'It may be contained individually or in combination of 2 or more types. Meanwhile, the aqueous polyurethane dispersion composition of the present invention may be applied to a substrate or a release sheet by a method such as bell coating, spray coating, roll coating, shower coating, or impregnation coating. It is heated at a temperature of 50 to 2501 or left at room temperature for a long time, and then dried to obtain a cured product. [Examples] Next, the present invention will be specifically described by way of examples and comparative examples. The hydroxyl value of the polycarbonate diol was measured by the method according to Jis K 1577. The acid value was measured in accordance with the B method of JIS K 1557. Moisture is determined by coulometric titration using a Karl Fischer moisture meter. The APHA is a Hazen unit color number (APHA) measured in accordance with JIS K 1557 in accordance with JIS K 0071-1 as follows. (Adjustment of standard solution) will gasify the acid clock 1. 245g, lead chloride · 6 hydrate 1.  〇〇〇g, 500 mL of water and 100 mL of hydrochloric acid were placed in a 1 L measuring flask, and after completely dissolving, water was added to a standard line to prepare a standard solution. This solution is equivalent to Apha 36 324043 8 201242984 v Standard Solution No.  500, various standard solutions are diluted with water this No.  Adjusted to 500 standard solutions. For example, APM standard solution No.  100 is water 80.  OmL dilution No.  500 standard solution 20.  Adjust with OmL. (Measurement method) A ratio of a common flat-bottomed flat glass tube of the same diameter and the same diameter as the inner diameter of 23 mm, which is colorless and transparent, and has a diameter of 23 mm, and the ratio of the marking line from the bottom to the same height as the liquid amount becomes 100 mL. In the color tube, carefully place the sample without blistering until the line is marked. Then, it is placed on a whiteboard in parallel with an appropriate APHA standard solution, and after visual comparison, the standard solution closest to the concentration of the sample is obtained, and the number of the standard solution is taken as APHA. The conversion ratio of the isocyanate group at the time of synthesis of the polyurethane compound was calculated from the isocyanate group content ratio measured by the method of JIS K 1603. The solid concentration of the polyurethane compound solution was 14 Torr. (: After the polyurethane ester solution was dried for 3 hours, it was calculated from the weight before and after drying. The viscosity was measured by an E-type viscosity meter. The hardness of the polyurethane compound was obtained by using an ultraviolet curing device (manufactured by SEN Special Light Source Co., Ltd., HM15001C~ 4, the lamp: SE-1500M).

The hardness of the cured product was measured by placing a coating sample prepared on a glass plate on a sample stage, and measuring the amplitude decay time by a pendulum hardness tester (a single pendulum hardness tester manufactured by BYK_Gardner GmbH). The longer the amplitude decay time, the greater the hardness. The elastic modulus, the tensile strength, and the elongation at break of the cured product were measured in accordance with the method of JIS K 7311 after the coated sample prepared on a polystyrene resin sheet was formed into a film shape. At the same time, the measurement was carried out under the measurement conditions of a temperature of 2 generations, a wetness of 5 〇%, and a 324043 37 201242984 stretching speed of 1 〇 Omm/min. The abrasion resistance of the cured product was set on a sample stage by using a coating film sample prepared on a polycarbonate resin sheet, and using a Taber abrasion tester (HS) manufactured by T0Y0SEIKI Co., Ltd. at a rotation speed of 6 rpm. Load: 5〇〇g, wear wheel: H-18, measure the weight of the coating film. The less the reduced weight, the better the wear resistance. _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ ), 1,4-benzenedimethanol 65.2 (0.47111〇1), 1,6-hexanediol 167.2 cliff (1.41 mo 1), titanium tetrabutyl oxide 0.03g, under normal pressure, and 曱The mixture of the alcohol and dimethyl carbonate was decanted and subjected to a transesterification reaction for 6 hours. During this time, the reaction temperature was slowly raised from 95 ° C to 2 ° C, and the composition of the distillate was adjusted to form an azeotropic composition of decyl alcohol and dinonyl carbonate or a composition thereof. Then, the pressure was gradually reduced to 100 mmHg, and the mixture of methanol and dimethyl carbonate was distilled off while stirring, and the transesterification reaction was further carried out at 195 ° C for 4 hours. After the completion of the reaction (after the completion of the decyl alcohol and the hydrazine carbonate), the reaction solution was cooled to room temperature to obtain 280 g of a polycarbonate diol copolymer. At the same time, the transesterification reaction was carried out in a nitrogen stream. The obtained polycarbonate diol copolymer had a number average molecular weight of 996, an APHA of 60, a hydroxyl value of 112·6 mg K0H/g, an acid value of 0.01 mg KOH/g, and a water content of i20 ppm. (2) The polycarbonate diol copolymer obtained in the above (1) was charged in a 199. 2g. The diol diol copolymer obtained in the above (1) was added to a 199. 2g. (g. 20mol), butyl acetate 224. lg, after the reaction temperature is set to 70 ° C, adding tetraethyl hydrazine acetone zirconium 〇. l〇g, isophorone diisocyanate 89. 3g (0.40 mol), in the reaction The reaction was carried out at a temperature of 80 ° C to 90 ° C until the conversion of the isocyanate group became 50%. Then, p-methoxyphenol 0. 34 g, tetraethylguanidinium oxime was added. I3g, ethylene glycol monoacrylate 48.9 g (0.42 mol) was reacted at a reaction temperature of 80 ° C to 90 ° C until the conversion of the isocyanate group became 99% or more. The solid content of the obtained polyamine ester compound in butyl acetate solution was 61%, and the viscosity was 211 cp / 40 °C. (3) Production of a polyurethane composition and a cured product: 1 part by weight of bis(2,4,6-trimercaptobenzylidene)phenylphosphine oxide and 19 parts by weight of ethyl acetate are sufficiently mixed with the above After 80 parts by weight of the butyl acetate solution of the polyurethane compound obtained in (2) was sufficiently mixed, a polyurethane composition (curable resin composition) was prepared. This curable resin composition was applied onto a glass plate using a 5 〇vm applicator, dried at 8 ° C for 30 minutes, and then irradiated with ultraviolet rays, and 紫外线mJ/cm 2 of ultraviolet rays. Hardened matter. The hardness of the obtained cured product was 111 seconds at the time of the amplitude decay time. (4) Synthesis of aqueous polyurethane dispersion 27.9 g (0.028 raol), 2,2-dihydroxyl of the polycarbonate diol copolymer obtained in the above (1) in a reaction apparatus equipped with a mixer and a heater曱Mercaptopropionate) 1^^'11.1§) and isophora-diisocyanate (;1?1)1,57» in N-ethyltetrahydropyrrolidone (43. 9g) in tetraethyl acetonide 5小时。 In the presence of 鍅13g 324043 39 201242984 'in a nitrogen atmosphere, heated at 80 to 90 ° C 2. 5 hours. Add 2,6-di-t-butyl-4-methylphenol (0.2 g) and 4-methoxyphenol (〇.2g) to change the ambient to air. Further, ethylene glycol monoacrylic acid vinegar 48.9 g (〇. 42 mol), dipentaerythritol hexaacrylate (DPHA, 79.9 g) and diethylamine (8.9 g) were added/mixed. The reaction mixture (226 g) was added to water (386 g) under vigorous stirring to obtain an aqueous polyurethane resin dispersion. [Example 2] A compound in which 1 part by weight of bis(2,4,6-trimethyl beryllyl)phenylphosphonium oxide was sufficiently mixed with 19 parts by weight of 2-hydroxyethyl methacrylate, and Examples 1 (2) The butyl acetate solution of the obtained polyurethane ester compound is sufficiently mixed in a weight ratio to prepare a polyurethane composition (curable resin composition). This polyurethane composition was applied onto a glass plate using a 50/m applicator, dried at 80 ° C for 30 minutes, and then irradiated with ultraviolet rays of 1,000 mJ/cm 2 by an ultraviolet curing device to obtain a cured product. The hardness of the obtained hardened material was 162 seconds in the amplitude decay time, the elastic modulus was 21 MPa, the tensile strength was 27 MPa, the breaking point elongation was 89%, and the abrasion resistance was reduced by 400 times. It is 32. 9mg. [Comparative Example 1] (1) Synthesis of Polyurethane Compound In a 000, 000 mL glass separation flask equipped with a stirrer, a thermometer, and a cooling tube, a polycarbonate diol (manufactured by Ube Industries, Ltd., trade name: ETERNACOLL UH-100, 1, polycarbonate diol obtained by reaction of hexane diol with dimethyl acid cleavage 'number average molecular weight 〇〇 4, APHA 10, hydroxyl value in · 7mgK0H / g, acid value 〇. 〇 2 mg KOH / g, water 324043 40 8 201242984 ¥ 400ppm) 200. 8g (〇. 20mol), butyl acetate 224. lg, after the reaction temperature is set at 70 ° C, adding tetraethyl hydrazine acetone 〇. g, isophorone diisan cyanate 90. Og (〇·4〇mol), at a reaction temperature of 8 (TC to 9 (TC). The reaction until the conversion of the isocyanate group becomes 50%. Then , the reaction is carried out at a reaction temperature of 80 ° C to 90 ° C by adding p-methoxyphenol 0. 34 g, tetraethyl sulfonium oxalate zirconium hydride, ethylene glycol monoacrylate 50. 0 g (0.43 mol). The conversion of the isocyanate group was 99% or more. The solid content of the obtained butyl acetate solution of the polyurethane compound was 62%, and the viscosity was i92 cp / 40 ° C. (2) Production of a polyurethane composition and a cured product: 1 part by weight of bis(2,4,6-trimethylbenzylidene)phenylphosphonium oxide and 19 parts by weight of ethyl acetate, and the above-mentioned (1) 80 parts by weight of a butyl acetate solution of the polyurethane compound obtained in the above) was sufficiently mixed to prepare a polyurethane composition (curable resin composition). The polyurethane composition was coated on a glass plate using a 50# application machine to 8 After 干燥°c was dried for 30 minutes, the ultraviolet ray of 〇〇〇mj/cm2 was irradiated with an ultraviolet ray curing device to obtain a cured product. The hardness of the obtained cured product was 52 seconds at the time of amplitude decay. [Comparative Example 2] a substance in which bis(2,4,6-trimercaptophenyl)phenylphosphine oxide hydrazine is sufficiently mixed with 19 parts by weight of 2-hydroxyethyl methacrylate, and obtained in Comparative Example 1 (1) After the 8 parts by weight of the polyvinyl acetate solution of the polyurethane compound was sufficiently mixed, the mixture was prepared to form a polyurethane composition (curable resin composition). The polyurethane composition was separately coated on a glass plate using a 50 applicator to dry at 80 ° C. After 30 minutes, hard UV The device was irradiated with ultraviolet light of 324043 41 201242984 1,000 mJ/cm 2 to obtain a cured product. The hardness of the obtained cured product was 55 seconds with an amplitude decay time, an elastic modulus of 46 MPa, a tensile strength of 27 MPa, and a break point elongation. When the amount is 13%, the weight loss is 55. 8 mg when the number of rotations is 400. [Industrial Applicability] The polyurethane ester compound, the aqueous polyurethane dispersion, and the polyurethane solution of the present invention can be used as an energy ray-curable paint or A material such as an energy ray hardenable coating agent. The polyurethane composition of the present invention can also be used as a raw material or a coating/coating agent itself as an energy ray-hardening coating or an energy ray-curing coating agent. The hardener of the present invention can be used as a film in various fields such as a decorative film or a cutting film. [Simple diagram description] None [Main component symbol description] None 324043 42 8

Claims (1)

201242984 VII. Patent application range: 1. A polyurethane ester compound which is a polycarbonate diol (A) having at least one repeating unit represented by the following formula (1) and having one hydroxyl group at each end of the molecular chain, The polyisocyanate compound (B) is obtained by reacting a (meth) acrylate compound (C) having one or more hydroxyl groups in the molecule; (wherein Z1 and Z2 each independently represent a linear or branched bond of a carbon number of 1 to 10). 2. The polyurethane compound according to claim 1, wherein the polycarbonate diol (A) has a repeating unit represented by the formula (1) and a repeating unit represented by the formula (2), and two of the molecular chains Each end has one hydroxyl group; (wherein Z3 represents a linear or branched alkanediyl group having 2 to 10 carbon atoms which may have a substituent, a cycloalkyldiyl group having 3 to 10 carbon atoms which may have a substituent, or may have a substituent Any one of the alkanediyl groups having an alicyclic structure having 5 to 10 carbon atoms in the main chain). 3. The polyurethane compound according to any one of claims 1 to 2, which is obtained by reacting an acid group-containing polyol (D). 4. The polyurethane compound according to any one of claims 1 to 3, which is obtained by reacting a chain extender (E). 324043 1 201242984 5 - An aqueous polyurethane dispersion which is a dispersion of a polyurethane compound according to any one of claims 1 to 4 of the present invention, at least in an aqueous medium. A polyurethane solution in which at least an organic solvent is dispersed or dissolved in the polyurethane compound according to any one of claims 1 to 4 of the patent application. The polyurethane ester compound, the polymerization initiator (G), and optionally the compound (F) having a polymerizable unsaturated bond, as described in any one of the above items. A cured product which is obtained by hardening a polyurethane composition as described in claim 7 of the patent application. An aqueous polyurethane dispersion composition which is a polymerizable unsaturated bond which is required for at least the polyurethane ester compound and the polymerization initiator (G) described in any one of claims 1 to 4; The compound is dispersed in an aqueous medium. The cured product is obtained by coating the aqueous composition described in item 9 of the patent application scope, and drying and hardening the composition. 11. A method for producing a polyvalent compound as described in the above-mentioned patent scope, which comprises reacting a polycarbonate diol (4) with a polyisocyanate compound (8) to obtain a polyisocyanate group at the terminal. The amine vinegar prepolymer is then 'reacted with the (meth) acrylate compound (c) having more than one thiol group in the molecule. 12. A method for producing a polyurethane compound as described in claim 3, which is to make a polycarbonate diol (4), a polyisocyanate compound 324043 2 201242984 (B), and a polyol having an acidic group. (D) The reaction is carried out to obtain a polyurethane prepolymer having an isocyanate group at the terminal, and then reacting the aforementioned polyurethane prepolymer with a (fluorenyl) acrylate compound (C) having one or more hydroxyl groups in the molecule. A method for producing a polyurethane compound as described in claim 4, which comprises a polycarbonate diol (A), a polyisocyanate compound (B) and optionally an acidic group-containing polyol ( D) reaction, obtaining a polyurethane prepolymer having an isocyanate group at the end, reacting the chain extender (E), and then reacting with a (mercapto)acrylic acid compound (C) having one or more hydroxyl groups in the molecule . A method for producing an aqueous polyurethane dispersion as described in claim 5, which comprises a polycarbonate diol (A), a polyisocyanate compound (B) and an acid group-containing polyol (D). After the reaction, the polyurethane prepolymer having an isocyanate group at the end is obtained, and the acidic group derived from the acidic group-containing polyol is neutralized and dispersed in an aqueous medium, optionally with a chain extender (E). The reaction is then carried out by reacting with a (fluorenyl) acrylate compound (C) having one or more hydroxyl groups in the molecule. A method for producing a polyurethane solution as described in claim 6, wherein the polycarbonate diol (A), the polyisocyanate compound (B) and, if necessary, an acidic group-containing polyol (D) After reacting in an organic solvent to obtain a polyurethane prepolymer having an isocyanate group at the end, it is reacted with a chain extender (E) as needed, and a (meth) acrylate compound having one or more hydroxyl groups in the molecule. (C) Reaction. 324043 3 201242984 IV. Designated representative map: (1) The representative representative map of this case is: (). (There is no picture in this case) (2) The symbol of the symbol of this representative figure is simple: (none) 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: 324043 3